Concept: Phases of matter
In this study, we have generated and characterized Electronic Cigarette (EC) aerosols using a combination of advanced technologies. In the gas phase, the particle number concentration (PNC) of EC aerosols was found to be positively correlated with puff duration whereas the PNC and size distribution may vary with different flavors and nicotine strength. In the liquid phase (water or cell culture media), the size of EC nanoparticles appeared to be significantly larger than those in the gas phase, which might be due to aggregation of nanoparticles in the liquid phase. By using in vitro high-throughput cytotoxicity assays, we have demonstrated that EC aerosols significantly decrease intracellular levels of glutathione in NHOKs in a dose-dependent fashion resulting in cytotoxicity. These findings suggest that EC aerosols cause cytotoxicity to oral epithelial cells in vitro, and the underlying molecular mechanisms may be or at least partially due to oxidative stress induced by toxic substances (e.g., nanoparticles and chemicals) present in EC aerosols.
Phenolic compound profiles of 20 honeys of different botanical origin (eucalyptus, citrus, chestnut and linden) were obtained by high-performance liquid chromatography with ultraviolet detection after solid phase extraction, in order to evaluate the effectiveness of the fingerprint method for monofloral honey discrimination.
The paper presents the development of a multiple consecutive extraction method enabling the determination of the total amount of bisphenol A (BPA) released from porous polysulfone (PS) membranes in a hemodialyzer or hemoconcentrator under simulated-use conditions. The levels of BPA were determined using solid phase extraction (SPE) coupled with high performance liquid chromatography-mass spectrometry (HPLC-MS). We demonstrated that it was difficult to determine the total amount of BPA released from the PS membranes using a single extraction method with finite solvent volume because of the chemical equilibrium between the extraction solution and the polymer phase. Repeated extractions gave more accurate results than a single extraction for the determination of the total amount of leachables in porous membranes. A general equation was derived to fit the elution profile of BPA released during multiple consecutive extractions.
Hot-melt extrusion is gaining importance for the production of amorphous solid solutions; in parallel, predictive tools for estimating drug solubility in polymers are increasingly demanded. The Hansen solubility parameter (SP) approach is well acknowledged for its predictive power of the miscibility of liquids as well as the solubility of some amorphous solids in liquid solvents. By solely using the molecular structure, group contribution (GC) methods allow the calculation of Hansen SPs. The GC parameter sets available were derived from liquids and polymers which conflicts with the object of prediction, the solubility of solid drugs. The present study takes a step from the liquid based SPs towards their application to solid solutes. On the basis of published experimental Hansen SPs of solid drugs and excipients only, a new GC parameter set was developed. In comparison to established parameter sets by van Krevelen/Hoftyzer, Beerbower/Hansen, Breitkreutz and Stefanis/Panayiotou, the new GC parameter set provides the highest overall predictive power for solubility experiments (correlation coefficient r=-0.87 to -0.91) as well as for literature data on melt extrudates and casted films (r=-0.78 to -0.96).
Chemical bond breaking and formation during chemical reactions can be observed using “transition state spectroscopy”. Comparing the measurement result of the transition state spectroscopy with the simulation result of single direct-dynamics trajectory, we have elucidated the reaction dynamics of Claisen rearrangement of allyl vinyl ether. Observed the reaction of the neat sample liquid, we have estimated the time constants of transformation from straight-chain structure to aromatic-like six-membered ring structure forming the C1-C6 bond. The result clarifies that the reaction proceeds via three steps taking longer time than expected from the gas phase calculation. This finding provides new hypothesis and discussions, helping the development of the field of reaction mechanism analysis.
A set of six dipeptides containing pyrrolysine invariably at their N-terminal positions is studied in gas and aqueous phase using a polarizable continuum model (PCM). The molecular geometries of the dipeptides are fully optimized at B3LYP/6-31++G(d,p) level of theory and a second derivative (frequency) analysis confirms that all the optimized geometries are true minima. The effects of solvation and identity of the varying C-terminal residue on the energetics, structural features of the peptide planes, values of the ψ and ϕ dihedrals, geometry around the α-carbon atoms and theoretically predicted vibrational spectra of the dipeptides are thoroughly analyzed. Solvation effects are found to modify the gas phase conformation of the dipeptides around ψ dihedrals while the identity of the varying C-terminal residue affect the values of ϕ, planarity of the peptide planes and geometry around the α-carbon atoms. The presence or absence of three types of intramolecular H-bonds, namely O…H-N, N…H-N and O…H-C that leave noticeable signatures in the IR spectra, play crucial roles in influencing the geometry of the peptide planes and in determining the energetics of the dipeptides.
- Langmuir : the ACS journal of surfaces and colloids
- Published over 2 years ago
Line tension could affect the contact angle at triple junction, especially in micro- to nano-scale wetting. We have developed an adaptive phase field model to consider the line tension quantitatively. This model is coupled with the smoothed boundary method for treating the contact line with the solid phase, while the volume constraint is imposed. Our calculated contact angles are in good agreement with the modified Young’s equation. Further examples are illustrated for the anisotropic wetting on hydrophilic/hydrophobic stripes and rectangular grooves.
Here we used organic composition and stable isotopic analysis to evaluate the effects of drainage and restoration at an ombrotrophic peatland, to assess whether rewetting of blanket bogs will reverse degradation. The organic composition of the peat and the isotopic fractionation between the solid (peat), liquid (pore water) and gas (soil gas) phases on actively accumulating, degrading and restored locations are compared. Fourier Transform Infrared Spectroscopy (FTIR) analysis of the organic material has shown a high level of humification (low decomposition) in the active peat. Stable isotope analysis in the solid, liquid and gas phases has corresponded with this and indicated that the active location is enriched in (13)C in the solid and gas phases, (15)N in the solid phase, (18)O in the liquid and gas phases and D in the liquid phase, suggesting a closed system with limited isotopic fractionation and thus limited water movement and decomposition. The degrading location has a lower level of humification, and is depleted in (13)C in the solid phase due to ingression of vascular plants. The restored location has high humification and enrichment of (13)C and (15)N in the solid phase, and D in the liquid phase suggesting increased microbial activity. (13)C and (18)O in the gas phase and (18)O in the liquid phase are depleted, as a result of microbial mediated gas production and rewetting. FTIR analysis has also indicated a subsurface zone of increased decomposition between the acrotelm and catotelm in both the active and degrading peat. This is due to a stable water table and is not present within the restored location, which we attribute to water table fluctuation associated with rewetting. This zone of increased decomposition adds to the complexity of blanket bog peatlands and the assumption that all systems can be generalized under one conceptual model.
The concept of a supersolid state combines the crystallization of a many-body system with dissipationless flow of the atoms from which it is built. This quantum phase requires the breaking of two continuous symmetries: the phase invariance of a superfluid and the continuous translational invariance to form the crystal. Despite having been proposed for helium almost 50 years ago, experimental verification of supersolidity remains elusive. A variant with only discrete translational symmetry breaking on a preimposed lattice structure-the ‘lattice supersolid’-has been realized, based on self-organization of a Bose-Einstein condensate. However, lattice supersolids do not feature the continuous ground-state degeneracy that characterizes the supersolid state as originally proposed. Here we report the realization of a supersolid with continuous translational symmetry breaking along one direction in a quantum gas. The continuous symmetry that is broken emerges from two discrete spatial symmetries by symmetrically coupling a Bose-Einstein condensate to the modes of two optical cavities. We establish the phase coherence of the supersolid and find a high ground-state degeneracy by measuring the crystal position over many realizations through the light fields that leak from the cavities. These light fields are also used to monitor the position fluctuations in real time. Our concept provides a route to creating and studying glassy many-body systems with controllably lifted ground-state degeneracies, such as supersolids in the presence of disorder.
We report the manufacture of novel graphene diode sensors (GDS), which are composed of monolayer graphene on silicon substrates, allowing exposure to liquids and gases. Parameter changes in the diode can be correlated with charge transfer from various adsorbates. The GDS allows for investigation and tuning of extrinsic doping of graphene with great reliability. The demonstrated recovery and long term stability qualifies the GDS as a new platform for gas, environmental, and bio-compatible sensors.