Optical forces arising from phase gradients

We demonstrate both theoretically and experimentally that phase gradients in a light field can be used to create a new category of optical traps complementary to the more familiar intensity-gradient traps known as optical tweezers. We further show that the work done by phase-gradient forces is path dependent and briefly discuss some ramifications of this nonconservativity.     

Single-walled carbon nanotubes embedded in oriented polymeric nanofibers by electrospinning

The electrospinning process was used successfully to embed single-walled carbon nanotubes (SWCNTs) in a poly(ethylene oxide) (PEO) matrix, forming composite nanofibers. Initial dispersion of SWCNTs in water was achieved by the use of an amphiphilic alternating copolymer of styrene and sodium maleate. The resulting dispersions were stable, having a dark, smooth, ink-like appearance. For electrospinning, the dispersions were mixed with PEO solution in an ethanol/water mixture. The distribution and conformation of the nanotubes in the nanofibers were studied by transmission electron microscopy (TEM). Oxygen plasma etching was used to expose the nanotubes within the nanofibers to facilitate direct observation. Nanotube alignment within the nanofibers was shown to depend strongly on the quality of the initial dispersions. Well-dispersed and separated nanotubes were embedded in a straight and aligned form, while entangled nonseparated nanotubes were incorporated as dense aggregates. X-ray diffraction demonstrated a high degree of orientation of the PEO crystals in the electrospun nanofibers with embedded SWCNTs. This result is in pronounced distinction to the detrimental effect of incorporation of multiwalled carbon nanotubes on polymer orientation in electrospun nanofibers, as reported previously.     

Characterization of water distribution in bread during storage using magnetic resonance imaging

A soy bread of fully acceptable quality and containing 49% soy ingredients (with or without 5% almond powder) has been recently developed in our laboratory.

An investigation on water distribution and mobility, as probed by proton signal intensity and T₂ magnetic resonance images, during storage was designed to examine possible relations between water states and hindered staling rate upon soy or soy–almond addition.

Water proton distribution throughout soy-containing loaves was found to be very homogeneous in fresh breads with and without almond, with minimal water migration occurring during prolonged storage. In contrast, traditional wheat bread displayed an inhomogeneous water proton population that tended to change (with higher moisture migration towards the outer perimeter of the slice) during storage. Similar results were found for water mobility throughout the loaves, as depicted in T₂ images. On intensity images of all considered bread varieties, the outer perimeter corresponding to the crust exhibited lower signal intensity due to decreased water content. Higher T₂ values were found in the crust of soy breads with and without almond, which were attributed to lipids.

The results indicated that the addition of soy to bread improved the homogeneous distribution of water molecules, which may hinder the staling rate of soy-containing breads. However, incorporation of almond had little effect on the water proton distribution or mobility of soy breads.     

Triggered release of aqueous content from liposome-derived sol-gel nanocapsules

Liposomes prepared from a mixture of L-alpha-dipalmitoylphosphatidylcholine and the PEGilated phospholipid N-(carbonylmethoxypoly(ethylene glycol 2000))-1,2-distearoyl-sn-glycero-3-phosphoethanolamine were used as templates for the production of silica and alkylated silica approximately 100 nm capsules, "liposils", entrapping aqueous solutions of anionic dyes. Triggered release of this content was successfully affected by either low-frequency ultrasound or by microwave treatments. Cryo-TEM was used to follow the formation process of these particles, which are aggregated in a chain-like manner. A mechanism explaining this phenomenon is suggested.     

Anion-binding properties of the tripyrrolemethane group: a combined experimental and theoretical study

Tripyrrolemethane- and bistripyrrolemethane-containing systems were recently reported to be efficient and selective hosts for anions. Nevertheless, the basic intrinsic properties of tripyrrolemethane as a ligand for anions have not yet been explored. Here we report the study of the anion-binding properties of the tripyrrolemethane group. We applied a combined experimental and theoretical approach to determine the affinity of the tripyrrolemethane system for different anions in the gas phase, in solution and in the crystalline state. In the crystal, the tripyrrolemethane group forms a number of different complexes with the bromide ion, some involving the participation of more than one ligand species. Despite the very similar basicity of fluoride and dihydrogen phosphate, the tripyrrolemethane ligand exhibits a clear preference for the fluoride anion in solution, which indicates an anion-binding system and not merely deprotonation. Although the affinity of the tripyrrolemethane ligand for other ions was negligible in solution, gas-phase studies show that complexation with larger halide ions is favoured over complexation with fluoride.     

Iron Borohydride Pincer Complexes for the Efficient Hydrogenation of Ketones under Mild,Base‐Free Conditions: Synthesis and Mechanistic Insight

The new, structurally characterized hydrido carbonyl tetrahydridoborate iron pincer complex [(iPr‐PNP)Fe(H)(CO)(η¹‐BH₄)] ( 1 ) catalyzes the base‐free hydrogenation of ketones to their corresponding alcohols employing only 4.1 atm hydrogen pressure. Turnover numbers up to 1980 at complete conversion of ketone were reached with this system. Treatment of 1 with aniline (as a BH₃ scavenger) resulted in a mixture of trans‐[(iPr‐PNP)Fe(H)₂(CO)] ( 4 a ) and cis‐[(iPr‐PNP)Fe(H)₂(CO)] ( 4 b ). The dihydrido complexes 4 a and 4 b do not react with acetophenone or benzaldehyde, indicating that these complexes are not intermediates in the catalytic reduction of ketones. NMR studies indicate that the tetrahydridoborate ligand in 1 dissociates prior to ketone reduction. DFT calculations show that the mechanism of the iron‐catalyzed hydrogenation of ketones involves alcohol‐assisted aromatization of the dearomatized complex [(iPr‐PNP*)Fe(H)(CO)] ( 7 ) to initially give the Fe⁰ complex [(iPr‐PNP)Fe(CO)] ( 21 ) and subsequently [(iPr‐PNP)Fe(CO)(EtOH)] ( 38 ). Concerted coordination of acetophenone and dual hydrogen‐atom transfer from the PNP arm and the coordinated ethanol to, respectively, the carbonyl carbon and oxygen atoms, leads to the dearomatized complex [(iPr‐PNP*)Fe(CO)(EtO)(MeCH(OH)Ph)] ( 32 ). The catalyst is regenerated by release of 1‐phenylethanol, followed by dihydrogen coordination and proton transfer to the coordinated ethoxide ligand.     

Photolysis of methyl-parathion thin films: Products,kinetics and quantum yields under different atmospheric conditions

The present study focuses on the photodegradation of methyl-parathion thin films, an organophosphate insecticide, under different atmospheric conditions. The latter include nitrogenated, oxygenated and ozonated atmospheres, under low and high relative humidity conditions. Addition of oxygen to the atmospheric mixture did not seem to affect the reaction rates and quantum yields. Relative humidity affect was minor, with a small enhancement in reaction rate under 254 nm radiation. The addition of ozone (to either dry or humid atmosphere), at all concentrations tested, largely enhanced degradation rates. In the absence of ozone, the obtained quantum yields for photolysis of methyl-parathion thin films under 254 and 313 nm were 0.024 ± 0.007 and 0.012 ± 0.005, respectively. These values are higher than the values previously reported for solutions of methanol and water. Although the presence of molecular oxygen and water vapors did not seem to affect much the reaction rates, it did have a certain effect on the resulted products. More polar products were obtained under oxygenated and ozonated atmospheres, as well as dimers under ozone conditions. The reaction on thin films has yielded more toxic products than usually found in solutions, adding alkylphosphate esters in addition to the oxons formed normally.     

Small molecule correctors of F508del-CFTR discovered by structure-based virtual screening

Folding correctors of F508del-CFTR were discovered by in silico structure-based screening utilizing homology models of CFTR. The intracellular segment of CFTR was modeled and three cavities were identified at inter-domain interfaces: (1) Interface between the two Nucleotide Binding Domains (NBDs); (2) Interface between NBD1 and Intracellular Loop (ICL) 4, in the region of the F508 deletion; (3) multi-domain interface between NBD1:2:ICL1:2:4. We hypothesized that compounds binding at these interfaces may improve the stability of the protein, potentially affecting the folding yield or surface stability. In silico structure-based screening was performed at the putative binding-sites and a total of 496 candidate compounds from all three sites were tested in functional assays. A total of 15 compounds, representing diverse chemotypes, were identified as F508del folding correctors. This corresponds to a 3% hit rate, ~tenfold higher than hit rates obtained in corresponding high-throughput screening campaigns. The same binding sites also yielded potentiators and, most notably, compounds with a dual corrector-potentiator activity (dual-acting). Compounds harboring both activity types may prove to be better leads for the development of CF therapeutics than either pure correctors or pure potentiators. To the best of our knowledge this is the first report of structure-based discovery of CFTR modulators.     

Flavor and LHC searches for new physics

Uncovering the physics of electroweak symmetry breaking (EWSB) is the raison-d’etre of the LHC. Flavor questions, it would seem, are of minor relevance for this quest, apart from their role in constraining the possible structure of EWSB physics. In this short review article, we outline, using flavor-dependent slepton physics as an example, how flavor can affect both searches for supersymmetry, and future measurements aimed at understanding the nature of any new discoveries. If the production cross-sections for supersymmetry are relatively low, as indicated by the fact that it has not revealed itself yet in standard searches, the usual assumptions about the superpartner spectra need rethinking. Furthermore, one must consider more intricate searches, such as lepton-based searches, which could be susceptible to flavor effects. We start by reviewing the flavor structure of existing frameworks for mediating supersymmetry breaking, emphasizing flavor-dependent models proposed recently. We use the kinematic endpoints of invariant mass distributions to demonstrate how flavor dependence can impact both searches for supersymmetry and the Inverse Problem. We also discuss methods for measuring small-mass splittings and mixings at the LHC, both in models with a neutralino LSP and in models with a charged slepton (N)LSP.