Meltable Spin Transition Molecular Materials with Tunable Tc and Hysteresis Loop Width

Herein, we report a way to achieve abrupt high‐spin to low‐spin transition with controllable transition temperature and hysteresis width, relying not on solid‐state cooperative interactions, but utilizing coherency between phase and spin transitions in neutral Fe^II meltable complexes.     

Antibacterial and antifungal LDPE films for active packaging

Active antimicrobial packaging is a promising form of active packaging that can kill or inhibit microorganism growth in order to maintain product quality and safety. One of the most common approaches is based on the release of volatile antimicrobial agents from the packaging material such as essential oils. Due to their highly volatile nature, the challenge is to preserve the essential oils during the high‐temperature melt processing of the polymer, while maintaining high antimicrobial activity for a desired shelf life. This study suggests a new approach in order to achieve this goal. Antimicrobial active films are developed based on low‐density polyethylene (LDPE), organo‐modified montmorillonite clays (MMT) and carvacrol (used as an essential oil model). In order to minimize carvacrol loss throughout the polymer compounding, a pre‐compounding step is developed in which clay/carvacrol hybrids are produced. The hybrids exhibit a significant increase in the d‐spacing of clay and enhanced thermal stability. The resulting LDPE/(clay/carvacrol) films exhibit superior and prolonged antibacterial activity against Escherichia coli and Listeria innocua, while polymer compounded with pure carvacrol loses the antibacterial properties within days. The films also present an excellent antifungal activity against Alternaria alternata, used as a model plant pathogenic fungus. Furthermore, infrared spectroscopy analysis of the LDPE/(clay/carvacrol) system displayed significantly higher carvacrol content in the film as well as a slower out‐diffusion of the carvacrol molecules in comparison to LDPE/carvacrol films. Thus, these new films have a high potential for antimicrobial food packaging applications due to their long‐lasting and broad‐spectrum antimicrobial efficacy. Copyright © 2014 John Wiley & Sons, Ltd.     

Metal-free inorganic ligands for colloidal nanocrystals: S2-, HS-, Se2-, HSe-, Te2-, HTe-, TeS3(2-), OH-, and NH2- as surface ligands

All-inorganic colloidal nanocrystals were synthesized by replacing organic capping ligands on chemically synthesized nanocrystals with metal-free inorganic ions such as S(2-), HS(-), Se(2-), HSe(-), Te(2-), HTe(-), TeS(3)(2-), OH(-) and NH(2)(-). These simple ligands adhered to the NC surface and provided colloidal stability in polar solvents. The versatility of such ligand exchange has been demonstrated for various semiconductor and metal nanocrystals of different size and shape. We showed that the key aspects of Pearson's hard and soft acids and bases (HSAB) principle, originally developed for metal coordination compounds, can be applied to the bonding of molecular species to the nanocrystal surface. The use of small inorganic ligands instead of traditional ligands with long hydrocarbon tails facilitated the charge transport between individual nanocrystals and opened up interesting opportunities for device integration of colloidal nanostructures.     

Semiclassical instanton approach to calculation of reaction rate constants in multidimensional chemical systems

The semiclassical instanton approximation is revisited in the context of its application to the calculation of chemical reaction rate constants. An analytical expression for the quantum canonical reaction rate constants of multidimensional systems is derived for all temperatures from the deep tunneling to high-temperature regimes. The connection of the derived semiclassical instanton theory with several previously developed reaction rate theories is shown and the numerical procedure for the search of instanton trajectories is provided. The theory is tested on seven different collinear symmetric and asymmetric atom transfer reactions including heavy-light-heavy, light-heavy-light and light-light-heavy systems. The obtained thermal rate constants agree within a factor of 1.5-2 with the exact quantum results in the wide range of temperatures from 200 to 1500 K.     

Chemistry in Ukraine

In this special issue, we highlight recent advances in chemical research by scientists in Ukraine, as well as by their compatriots and collaborators outside the country. Besides spotlighting their contributions, we see our task in fostering global partnerships and multi-, inter-, and trans-disciplinary collaborations, including much-needed co-funded projects and initiatives. The three decades of the renewed Ukraine independence have seen rather limited integration of Ukrainian (chemical) science into global research communities.^[1] At the same time, the recent surge of collaborative science initiatives between European Union (EU) and Ukraine echoes the unfolding steps towards Ukraine's full research participation to the Horizon Europe Program. This recently implemented step opens enormous possibilities for Ukrainian researchers to apply for diverse EU research grants. Moreover, a number of journal special issues and collections were launched to highlight Ukrainian chemistry (i. e., by Chemistry of Heterocyclic Compounds^[2] and ChemistrySelect^[3]). Other scientific initiatives include ‘European Chemistry School for Ukrainians’^[4] and ‘Kharkiv Chemical Seminar’^[5] as voluntary projects aimed at engaging Ukrainian scientists into European and international chemical research.     

Zeolites with Continuously Tuneable Porosity

Zeolites are important materials whose utility in industry depends on the nature of their porous structure. Control over microporosity is therefore a vitally important target. Unfortunately, traditional methods for controlling porosity, in particular the use of organic structure‐directing agents, are relatively coarse and provide almost no opportunity to tune the porosity as required. Here we show how zeolites with a continuously tuneable surface area and micropore volume over a wide range can be prepared. This means that a particular surface area or micropore volume can be precisely tuned. The range of porosity we can target covers the whole range of useful zeolite porosity: from small pores consisting of 8‐rings all the way to extra‐large pores consisting of 14‐rings.     

A theory of rheed

Elastic Reflection High Energy Electron Diffraction (RHEED) by solid surfaces is studied theoretically. First, the problem of finding the electron reflection and transmission coefficients of a crystal slab is formally solved. Following this, it is shown how the formal solution may be used in a practical computation of the diffracted beam intensities. These two results are applied to a study of high energy (20 keV) electron diffraction by the Ag(001) surface. Rocking curves are computed to illustrate the dependence of the reflection coefficients on the glancing angle of the incident beam, the incident beam azimuth being in the [110] direction. The curves are shown to have several features in common with a typical set of LEED I-V plots: primary Bragg peaks, secondary Bragg peaks and resonance peaks are all present. The dependence of the reflection coefficients on the deviation of the incident beam azimuth from the [110] direction is also described. Additional computations are made to illustrate the sensitivity of the RHEED pattern to the details of the surface structure: the relative heights of the peaks in the rocking curves are shown to be quite sensitive to the spacing of the topmost atomic layers.     

Calculation of MEED intensities in the 5–10 keV electron energy range

A method for computing MEED intensities in the 5–10 keV electron energy range is described. The method is based on improving the computational efficiency of a RHEED program so that it can be used to handle the larger matrices involved in MEED calculations. As an example of its use rocking curves are computed for 5 keV electrons incident on the Al(110) surface in the 11?0 azimuth. Further numerical results are then presented to show that smaller scale calculations, in which only beams in the zeroth Laue zone are taken into account, can give a useful approximation to the exact rocking curves. Finally, the conditions under which these calculations are likely to be valid are discussed.     

RHEED from stepped surfaces and its relation to RHEED intensity oscillations observed during MBE

Multiple scattering theory is used to calculate the intensities of reflection high energy electron diffraction from periodic arrays of surface steps. The intensities are found to depend strongly on the direction of the incident beam azimuth. When the incident beam azimuth is parallel to the step edges, both the specular and diffracted beam intensities are diminished with respect to the intensities from a flat surface. When the incident beam azimuth is perpendicular to the edges, the intensities of all the beams are of the same order of magnitude as for a flat surface but some of the peak heights are oscillatory functions of the number of atoms in the topmost layer. These peak intensity oscillations are very similar to the intensity oscillations observed during molecular beam epitaxial film growth.