Efficient, Scalable, and Solvent-free Mechanochemical Synthesis of the OLED Material Alq(3) (q=8-Hydroxyquinolinate)

The aluminum complex Alq(3) (q = 8-hydroxyquinolinate), which has important applications in organic light-emitting diode materials, is shown to be readily synthesized as a pure phase under solvent-free mechanochemical conditions from Al(OAc)(2)OH and 8-hydroxyquinoline by ball milling. The initial product of the mechanochemical synthesis is a novel acetic acid solvate of Alq(3), and the alpha polymorph of Alq(3) is obtained on subsequent heating/desolvation of this phase. The structure of the mechanochemically prepared acetic acid solvate of Alq(3) has been determined directly from powder X-ray diffraction data and is shown to be a different polymorph from the corresponding acetic acid solvate prepared by solution-state crystallization of Alq(3) from acetic acid. Significantly, the mechanochemical synthesis of Alq(3) is shown to be fully scalable across two orders of magnitude from 0.5 to 50 g scale. The Alq(3) sample obtained from the solvent-free mechanochemical synthesis is analytically pure and exhibits identical photoluminescence behavior to that of a sample prepared by the conventional synthetic route.

Mechanochemical interconversion between discrete complexes and coordination networks - formal hydration/dehydration by LAG

Using a small planetary ball mill, liquid-assisted grinding (LAG) of metal salts or oxides (ZnO, CdO, CdCO3, Cu(OAc)(2)center dot H2O, Co(OAc)(2)center dot 4H(2)O, Mn(OAc)(2)center dot 4H(2)O, Ni(OAc)(2)center dot 4H(2)O, FeSO4 center dot 7H(2)O) with two equivalents of isonicotinic acid (HINA) and small amounts of water ( up to 5.6 molar equivalents) gave discrete aquo complexes trans-[M(INA)(2)(OH2)(4)] (M = Zn, Cd, Cu, Fe, Co, Ni, Mn) efficiently within 30 min. For M = Zn, Cd and Cu these complexes readily undergo reversible formal dehydration to the extended network structures [M(INA)(2)] (M = Zn, Cu) or [Cd(INA)(2)(OH2)]center dot DMF by further LAG with non-aqueous liquids such as methanol or DMF. Overall, the mechanochemical dehydrations are more effective than heating or immersion in bulk solvents. The work demonstrates a two-step mechanochemical synthesis of coordination networks via discrete aquo complexes which may be preferable to single step reactions or grinding-annealing procedures in some cases. For example, the two step method was the only way to prepare [Cd(INA)(2)(OH2)]center dot DMF mechanochemically and the porous network Cu(INA)(2) could not be obtained from the aquo complex by heating.

Microstructure, properties and application of YAl2 intermetallic compound as particle reinforcements

An yttrium aluminum (YAl2) intermetallic compound ingot was prepared in an induction furnace under vacuum. The microstructure of YAl2 ingot was characterized by optical microscopy, scanning electron microscopy, and X-ray diffraction. The load bearing response of YAl2 intermetallic was investigated and compared with SiC ceramic by indentation combined with optical microscopy and scanning electron microscopy. Additionally, the tensile properties of the Mg–Li matrix composites reinforced with ultrafine YAl2 particles fabricated by planet ball milling were tested. The results show that the intermetallic compound ingot in this experiment is composed of a main face-centered-cubic structure YAl2 phase, a small amount of YAl phase, and minor Y and Al-rich phases. YAl2 intermetallic compound has excellent stability and shows better capability in crack resistance than SiC ceramic. The YAl2 intermetallic compound has better deformation compatibility with the Mg–14Li–3Al matrix than SiC reinforcement with the matrix, which leads to the superior resistance to crack for YAl2p/Mg–14Li–3Al composite compared to SiCp/Mg–14Li–3Al composite.

An EPID-based method for comprehensive verification of gantry, EPID and the MLC carriage positional accuracy in Varian linacs during arc treatments

Background

]In modern radiotherapy, it is crucial to monitor the performance of all linac components including gantry, collimation system and electronic portal imaging device (EPID) during arc deliveries. In this study, a simple EPID-based measurement method has been introduced in conjunction with an algorithm to investigate the stability of these systems during arc treatments with the aim of ensuring the accuracy of linac mechanical performance.

The Varian EPID sag, gantry sag, changes in source-to-detector distance (SDD), EPID and collimator skewness, EPID tilt, and the sag in MLC carriages as a result of linac rotation were separately investigated by acquisition of EPID images of a simple phantom comprised of 5 ball-bearings during arc delivery. A fast and robust software package was developed for automated analysis of image data. Twelve Varian linacs of different models were investigated.

The average EPID sag was within 1 mm for all tested linacs. All machines showed less than 1 mm gantry sag. Changes in SDD values were within 1.7 mm except for three linacs of one centre which were within 9 mm. Values of EPID skewness and tilt were negligible in all tested linacs. The maximum sag in MLC leaf bank assemblies was around 1 mm. The EPID sag showed a considerable improvement in TrueBeam linacs.

The methodology and software developed in this study provide a simple tool for effective investigation of the behaviour of linac components with gantry rotation. It is reproducible and accurate and can be easily performed as a routine test in clinics.

Water structure and chaotropicity: their uses, abuses and biological implications

The concept of "water structure" has been invoked to explain all manner of aqueous phenomena. Here we look at the origins of this tendency to understand solute hydration in terms of structural changes in bulk water, and consider the validity of one particular example: the classification of small solutes as chaotropic or kosmotropic, and the putative relation of this terminology to notions of structure-making and structure-breaking in the solvent. We doubt whether complex phenomena such as Hofmeister and osmolyte effects on macromolecules can be understood simply on the basis of a change in solvent structure. Rather, we argue that chaotropicity, if understood in the original sense, arises from the activities that solutes exert on macromolecular systems, as well as from deviations of solvation water from bulk-like behaviour. If applied judiciously, chaotropicity remains a potent, biologically pertinent parameter useful for classifying and understanding solution phenomena in all types of living system.

Mechanochemical preparation of Ag catalysts for the n-octane-SCR de-NOx reaction: Structural and reactivity effects

Mechanochemical preparation of Ag/Al2O3 catalysts used for the selective catalytic reduction of NOx using hydrocarbons has been shown to substantially increase the activity of the catalyst in comparison with Ag/Al2O3 prepared by wet impregnation. The effect of using different ball-milling experimental parameters on both the structure of the material as well as the catalyst activity has been investigated and the optimum conditions established. A phase transition from γ- to α-alumina was observed milling at high speeds which was found to result in lower catalyst activities. At lower milling speeds both fracturing and agglomeration of the alumina support can be observed depending on the grinding time. However, due to ball-milling, a general enhancement in the NOx reduction activity was observed for all catalysts compared with the conventionally prepared catalysts irrespective of the reductant used. Transient DRIFTS-MS experiments were performed to investigate the effect of H2 in the absence and presence of water on the SCR reaction over catalysts prepared by both ball milling and wet impregnation. In-situ DRIFTS-MS analysis revealed significant differences in both gas phase and surface species. Most notably, isocyanate species were formed significantly more quickly and at higher surface concentration in the case of the mechanochemically prepared catalyst.

Chaotropicity: a key factor in product tolerance of biofuel-producing microorganisms

Fermentation products can chaotropically disorder macromolecular systems and induce oxidative stress, thus inhibiting biofuel production. Recently, the chaotropic activities of ethanol, butanol and vanillin have been quantified (5.93, 37.4, 174kJkg(-1)m(-1) respectively). Use of low temperatures and/or stabilizing (kosmotropic) substances, and other approaches, can reduce, neutralize or circumvent product-chaotropicity. However, there may be limits to the alcohol concentrations that cells can tolerate; e.g. for ethanol tolerance in the most robust Saccharomyces cerevisiae strains, these are close to both the solubility limit (<25%, w/v ethanol) and the water-activity limit of the most xerotolerant strains (0.880). Nevertheless, knowledge-based strategies to mitigate or neutralize chaotropicity could lead to major improvements in rates of product formation and yields, and also therefore in the economics of biofuel production.

Size effect of graphene on electrocatalytic activation of oxygen

Crystals of graphite nanosheets, achieved via a simple ball milling approach, show a significant size effect in electrocatalytic activation of oxygen.

Concomitant osmotic and chaotropicity-induced stresses in Aspergillus wentii: compatible solutes determine the biotic window

Whereas osmotic stress response induced by solutes has been well-characterized in fungi, less is known about the other activities of environmentally ubiquitous substances. The latest methodologies to define, identify and quantify chaotropicity, i.e. substance-induced destabilization of macromolecular systems, now enable new insights into microbial stress biology (Cray et al. in Curr Opin Biotechnol 33:228–259, 2015a, doi:10.​1016/​j.​copbio.​2015.​02.​010; Ball and Hallsworth in Phys Chem Chem Phys 17:8297–8305, 2015, doi:10.​1039/​C4CP04564E; Cray et al. in Environ Microbiol 15:287–296, 2013a, doi:10.​1111/​1462-2920.​12018). We used Aspergillus wentii, a paradigm for extreme solute-tolerant fungal xerophiles, alongside yeast cell and enzyme models (Saccharomyces cerevisiae and glucose-6-phosphate dehydrogenase) and an agar-gelation assay, to determine growth-rate inhibition, intracellular compatible solutes, cell turgor, inhibition of enzyme activity, substrate water activity, and stressor chaotropicity for 12 chemically diverse solutes. These stressors were found to be: (i) osmotically active (and typically macromolecule-stabilizing kosmotropes), including NaCl and sorbitol; (ii) weakly to moderately chaotropic and non-osmotic, these were ethanol, urea, ethylene glycol; (iii) highly chaotropic and osmotically active, i.e. NH4NO3, MgCl2, guanidine hydrochloride, and CaCl2; or (iv) inhibitory due primarily to low water activity, i.e. glycerol. At ≤0.974 water activity, Aspergillus cultured on osmotically active stressors accumulated low-M r polyols to ≥100 mg g dry weight−1. Lower-M r polyols (i.e. glycerol, erythritol and arabitol) were shown to be more effective for osmotic adjustment; for higher-M r polyols such as mannitol, and the disaccharide trehalose, water-activity values for saturated solutions are too high to be effective; i.e. 0.978 and 0.970 (25 ºC). The highly chaotropic, osmotically active substances exhibited a stressful level of chaotropicity at physiologically relevant concentrations (20.0–85.7 kJ kg−1). We hypothesized that the kosmotropicity of compatible solutes can neutralize chaotropicity, and tested this via in-vitro agar-gelation assays for the model chaotropes urea, NH4NO3, phenol and MgCl2. Of the kosmotropic compatible solutes, the most-effective protectants were trimethylamine oxide and betaine; but proline, dimethyl sulfoxide, sorbitol, and trehalose were also effective, depending on the chaotrope. Glycerol, by contrast (a chaotropic compatible solute used as a negative control) was relatively ineffective. The kosmotropic activity of compatible solutes is discussed as one mechanism by which these substances can mitigate the activities of chaotropic stressors in vivo. Collectively, these data demonstrate that some substances concomitantly induce chaotropicity-mediated and osmotic stresses, and that compatible solutes ultimately define the biotic window for fungal growth and metabolism. The findings have implications for the validity of ecophysiological classifications such as ‘halophile’ and ‘polyextremophile’; potential contamination of life-support systems used for space exploration; and control of mycotoxigenic fungi in the food-supply chain.

Virtual Thrower Versus Real Goalkeeper: The Influence of Different Visual Conditions on Performance

In order to use virtual reality as a sport analysis tool, we need to be sure that an immersed athlete reacts realistically in a virtual environment. This has been validated for a real handball goalkeeper facing a virtual thrower. However, we currently ignore which visual variables induce a realistic motor behavior of the immersed handball goalkeeper. In this study, we used virtual reality to dissociate the visual information related to the movements of the player from the visual information related to the trajectory of the ball. Thus, the aim is to evaluate the relative influence of these different visual information sources on the goalkeeper's motor behavior. We tested 10 handball goalkeepers who had to predict the final position of the virtual ball in the goal when facing the following: only the throwing action of the attacking player (TA condition), only the resulting ball trajectory (BA condition), and both the throwing action of the attacking player and the resulting ball trajectory (TB condition). Here we show that performance was better in the BA and TB conditions, but contrary to expectations, performance was substantially worse in the TA condition. A significant effect of ball landing zone does, however, suggest that the relative importance between visual information from the player and the ball depends on the targeted zone in the goal. In some cases, body-based cues embedded in the throwing actions may have a minor influence on the ball trajectory and vice versa. Kinematics analysis was then combined with these results to determine why such differences occur depending on the ball landing zone and consequently how it can clarify the role of different sources of visual information on the motor behavior of an athlete immersed in a virtual environment.

Probing The effects of Experimental Conditions on the Character of Drug-Polymer Phase Diagrams Constructed Using Flory-Huggins Theory

Purpose: Amorphous drug-polymer solid dispersions have been found to result in improved drug dissolution rates when compared to their crystalline counterparts. However, when the drug exists in the amorphous form it will possess a higher Gibb’s free energy than its associated crystalline state and can recrystallize. Drug-polymer phase diagrams constructed through the application of the Flory Huggins (F-H) theory contain a wealth of information regarding thermodynamic and kinetic stability of the amorphous drug-polymer system. This study was aimed to evaluate the effects of various experimental conditions on the solubility and miscibility detections of drug-polymer binary system. Methods: Felodipine (FD)-Polyvinylpyrrolidone (PVP) K15 (PVPK15) and FD-Polyvinylpyrrolidone/vinyl acetate (PVP/VA64) were the selected systems for this research. Physical mixtures with different drug loadings were mixed and ball milled. These samples were then processed using Differential Scanning Calorimetry (DSC) and measurements of melting point (Tend) and glass transition (Tg) were detected using heating rates of 0.5, 1.0 and 5.0°C/min. Results: The melting point depression data was then used to calculate the F-H interaction parameter (χ) and extrapolated to lower temperatures to complete the liquid–solid transition curves. The theoretical binodal and spinodal curves were also constructed which were used to identify regions within the phase diagram. The effects of polymer selection, DSC heating rate, time above parent polymer Tg and polymer molecular weight were investigated by identifying amorphous drug miscibility limits at pharmaceutically relevant temperatures. Conclusion: The potential implications of these findings when applied to a non-ambient processing method such as Hot Melt Extrusion (HME) are also discussed.