Experimental study of exclusive 2H(e,e'p)n reaction mechanisms at high Q2

The reaction 2H(e,e'p)n has been studied with full kinematic coverage for photon virtuality 1.75NN transition is the primary contribution at higher momenta.     

Measurement of direct photon production in p+p collisions at sqrt[s] = 200 GeV

Cross sections for midrapidity production of direct photons in p+p collisions at the Relativistic Heavy Ion Collider (RHIC) are reported for transverse momenta of 3 < pT < 16 GeV/c. Next-to-leading order perturbative QCD (pQCD) describes the data well for pT >5 GeV/c, where the uncertainties of the measurement and theory are comparable. We also report on the effect of requiring the photons to be isolated from parton jet energy. The observed fraction of isolated photons is well described by pQCD for pT >7 GeV/c.     

Carbene stabilization by aryl substituents. Is bigger better?

The geometries and relative stabilities of the singlet and triplet states of phenyl- (Cs), diphenyl- (C2), 1-naphthyl- (Cs), di(1-naphthyl)- (C2), and 9-anthryl-substituted (Cs) carbenes were investigated at the B3LYP/6-311+G(d,p) + ZPVE level of density functional theory. The singlet-triplet energy separations (DeltaEST), 2.7, 2.9, 3.4, 3.7, and 5.7 kcal/mol, respectively, after including an empirical correction (2.8 kcal/mol) based on the error in the computed singlet-triplet gap for methylene versus experiment, are in good agreement with available experimental values. Consistent with literature reports, triplet di(9-anthryl)carbene has a linear, D2d symmetrical, allene structure with 1.336 A C=C bond lengths and considerable biradical character. B3LYP favors such cumulene biradical structures and triplet spin states and predicts a large (>15 kcal/mol) "di(9-anthryl)carbene" singlet-triplet (biradical) energy gap. The resonance stabilization of both singlet and triplet carbenes increases modestly with the size of the arene substituent and overall, (di)arylcarbenes, both singlet and triplet, are better stabilized by bigger substituents. For example, methylene is stabilized more by a naphthyl than a phenyl group (singlets, 26.6 versus 24.4; and triplets, 20.9 versus 18.1 kcal/mol, respectively). The carbene geometries are affected by both steric effects and arene-carbene orbital interactions (sigma-p and p-pi). For instance, the central angles at the carbene are widened by a second arene group, which leads to increased s-character and shorter carbene bond lengths (i.e., C-C, C-H). In general, the aromaticity of the substituted rings in triplet carbenes is most affected by the presence of the unpaired electrons.     

Steric effects in electron transfer from potassium to pi-bonded oriented molecules CH3CN, CH3NC, and CCl3CN

Electron transfer from K atoms to oriented CH3CN, CH3NC, and CCl3CN is studied in crossed beams at energies near the threshold for forming an ion pair. For the methyl compounds, the dominant ions are K+ and CN-; the steric asymmetry is very small and energy-independent, characteristic of sideways attack with the electron apparently entering the pi*CN antibonding orbital. Migration of the electron to the sigma*CC orbital to break the C-C bond is greatly facilitated by interaction with the atomic donor. CH2CN- is formed in collisions preferring CH3-end attack, and the steric asymmetry becomes very large near threshold. CCl3CN mostly forms Cl- in collisions slightly favoring the CCl3 end with a small energy dependence with the electron apparently entering the sigma* LUMO. CN- is formed in much smaller yield with a slight preference for the CN end. The parent negative ion CCl3CN- is observed, and a lower limit for its electron affinity is estimated to be 0.3 eV. Fragment ions CCl2CN- and CClCN- are also observed with upper limits for the quantity bond dissociation energy - electron affinity (BDE - EA) estimated to be 0.6 and 1.0 eV, respectively.     

Observation of long-range orientational order in monolayers of polydisperse colloids

Polydisperse amorphous-silicon colloidal particles ranging from approximately 10 to 140 nm in diameter were evaporated onto carbon substrates. The particles formed close-packed monolayers in which each particle had 6-fold nearest-neighbor coordination characteristic of a hexagonal lattice yet completely lacked positional order. Orientational correlation functions were calculated for the particles and found to be constant throughout the aggregate, indicating the occurrence of long-range orientational order. Computer simulations revealed that the structural organization in this system resulted from capillary immersion forces that lead to a size separation as the particles deposit from the evaporating solvent onto the substrate.     

Synthesis of bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) derivatives functionalised with two, four or eight hydroxyl groups

Short synthetic routes to a range of BEDT-TTF derivatives functionalised with two, four or eight hydroxyl groups are reported, of interest because of their potential for introducing hydrogen bonding between donor and anion into their radical cation salts. The cycloaddition of 1,3-dithiole-2,4,5-trithione with alkenes to construct 5,6-dihydro-1,3-dithiolo[4,5-b]1,4-dithiin-2-thiones is a key step, with homo- or hetero-coupling procedures and O-deprotection completing the syntheses. The first synthesis of a single diastereomer of tetrakis(hydroxymethyl)BEDT-TTF, the cis,trans product, was achieved by careful choice of O-protecting groups to facilitate separation of homo- and hetero-coupled products. Cyclisation of the trithione with enantiopure 1R,2R,5R,6R-bis(O,O-isopropylidene)hex-3-ene-1,2,5,6-tetrol (from D-mannitol) gave two separable diastereomeric thiones, which can be transformed to enantiomeric BEDT-TTF derivatives with four or eight hydroxyl groups.     

Discovery of novel catalytic materials for emissions control using high throughput scanning mass spectrometry

High-throughput approaches were applied to the discovery of more efficient catalysts for various applications in emissions control. The screening approach was based on a hierarchy of qualitative or semi-quantitative primary screens for discovery of hits and quantitative secondary screens for confirmation and scale-up of leads. In this work, primary screening was carried out by fast scanning mass spectrometry (SMS) for NO(x) abatement, low temperature CO oxidation, VOC removal, CO(x) methanation and the water gas shift (WGS) reaction.     

Long-range Lennard-Jones and electrostatic interactions in interfaces: application of the isotropic periodic sum method

Molecular dynamics (MD) simulations of heptane/vapor, hexadecane/vapor, water/vapor, hexadecane/water, and dipalmitoylphosphatidylcholine (DPPC) bilayers and monolayers are analyzed to determine the accuracy of treating long-range interactions in interfaces with the isotropic periodic sum (IPS) method. The method and cutoff (rc) dependences of surface tensions, density profiles, water dipole orientation, and electrostatic potential profiles are used as metrics. The water/vapor, heptane/vapor, and hexadecane/vapor interfaces are accurately and efficiently calculated with 2D IPS (rc=10 A). It is demonstrated that 3D IPS is not practical for any of the interfacial systems studied. However, the hybrid method PME/IPS [Particle Mesh Ewald for electrostatics and 3D IPS for Lennard-Jones (LJ) interactions] provides an efficient way to include both types of long-range forces in simulations of large liquid/vacuum and all liquid/liquid interfaces, including lipid monolayers and bilayers. A previously published pressure-based long-range LJ correction yields results similar to those of PME/IPS for liquid/liquid interfaces. The contributions to surface tension of LJ terms arising from interactions beyond 10 A range from 13 dyn/cm for the hexadecane/vapor interface to approximately 3 dyn/cm for hexadecane/water and DPPC bilayers and monolayers. Surface tensions of alkane/vapor, hexadecane/water, and DPPC monolayers based on the CHARMM lipid force fields agree very well with experiment, whereas surface tensions of the TIP3P and TIP4P-Ew water models underestimate experiment by 16 and 11 dyn/cm, respectively. Dipole potential drops (DeltaPsi) are less sensitive to long-range LJ interactions than surface tensions. However, DeltaPsi for the DPPC bilayer (845+/-3 mV proceeding from water to lipid) and water (547+/-2 mV for TIP4P-Ew and 521+/-3 mV for TIP3P) overestimate experiment by factors of 3 and 5, respectively, and represent expected deficiencies in nonpolarizable force fields.     

Cooperative and directional folding of the preQ1 riboswitch aptamer domain

Riboswitches are cis-acting RNA fragments that regulate gene expression by sensing cellular levels of the associated small metabolites. In bacteria, the class I preQ(1) riboswitch allows the fine-tuning of queuosine biosynthesis in response to the intracellular concentration of the queuosine anabolic intermediate preQ(1). When binding preQ(1), the aptamer domain undergoes a significant degree of secondary and tertiary structural rearrangement and folds into an H-type pseudoknot. Conformational "switching" of the riboswitch aptamer domain upon recognizing its cognate metabolite plays a key role in the regulatory mechanism of the preQ(1) riboswitch. We investigate the folding mechanism of the preQ(1) riboswitch aptamer domain using all-atom Go?-model simulations. The folding pathway of such a single domain is found to be cooperative and sequentially coordinated, as the folding proceeds in the 5' → 3' direction. This kinetically efficient folding mechanism suggests a fast ligand-binding response in competition with RNA elongation.     

The role of dimension in multivalent binding events: structure-activity relationship of dendritic polyglycerol sulfate binding to L-selectin in correlation with size and surface charge density

L ‐, P ‐, and E ‐Selectin are cell adhesion molecules that play a crucial role in leukocyte recruitment from the blood stream to the afflicted tissue in an acute and chronic inflammatory setting. Since selectins mediate the initial contact of leukocytes to the vascular endothelium, they have evolved as a valuable therapeutic target in diseases related to inflammation by inhibition of the physiological selectin–ligand interactions. In a previous study, it was demonstrated that dPGS, a fully synthetic heparin analogue, works as an efficient inhibitor towards L ‐ and P ‐selectin in vitro as well as in vivo. Herein, the focus is directed towards the effect of size and charge density of the polyanion. The efficiency of L ‐selectin inhibition via an SPR‐based in vitro assay and a cell‐based flow chamber assay is investigated with dPGS ranging from approximately 4 to 2000 kDa. SPR measurements show that the inhibitory potential of highly sulfated dPGS increases with size and charge density. Thereby, IC₅₀ values from the micromolar to the low picomolar range are determined. The same tendency could be observed in a cell‐based flow chamber assay with three representative dPGS samples. This structure–affinity relationship of dPGS suggests that the strong inhibitory potential of dPGS is not only based on the strong electrostatic interaction with areas of cationic surface potential on L ‐selectin but is also due to a steric shielding of the carbohydrate binding site by large, flexible dPGS particles.