Parton distributions and new physics searches: the Drell–Yan forward–backward asymmetry as a case study

We present the first unquenched lattice-QCD calculation of the form factors for the decay \(B\rightarrow D^*\ell \nu \) at nonzero recoil. Our analysis includes 15 MILC ensembles with \(N_f=2+1\) flavors of asqtad sea quarks, with a strange quark mass close to its physical mass. The lattice spacings range from \(a\approx 0.15\) fm down to 0.045 fm, while the ratio between the light- and the strange-quark masses ranges from 0.05 to 0.4. The valence b and c quarks are treated using the Wilson-clover action with the Fermilab interpretation, whereas the light sector employs asqtad staggered fermions. We extrapolate our results to the physical point in the continuum limit using rooted staggered heavy-light meson chiral perturbation theory. Then we apply a model-independent parametrization to extend the form factors to the full kinematic range. With this parametrization we perform a joint lattice-QCD/experiment fit using several experimental datasets to determine the CKM matrix element \(|V_{cb}|\). We obtain \(\left| V_{cb}\right| = (38.40 \pm 0.68_{\text {th}} \pm 0.34_{\text {exp}} \pm 0.18_{\text {EM}})\times 10^{-3}\). The first error is theoretical, the second comes from experiment and the last one includes electromagnetic and electroweak uncertainties, with an overall \(\chi ^2\text {/dof} = 126/84\), which illustrates the tensions between the experimental data sets, and between theory and experiment. This result is in agreement with previous exclusive determinations, but the tension with the inclusive determination remains. Finally, we integrate the differential decay rate obtained solely from lattice data to predict \(R(D^*) = 0.265 \pm 0.013\), which confirms the current tension between theory and experiment.

     

Direct interfacial Y731 oxidation in α2 by a photoβ2 subunit of E. coli class Ia ribonucleotide reductase

Proton-coupled electron transfer (PCET) is a fundamental mechanism important in a wide range of biological processes including the universal reaction catalysed by ribonucleotide reductases (RNRs) in making de novo, the building blocks required for DNA replication and repair. These enzymes catalyse the conversion of nucleoside diphosphates (NDPs) to deoxynucleoside diphosphates (dNDPs). In the class Ia RNRs, NDP reduction involves a tyrosyl radical mediated oxidation occurring over 35 Å across the interface of the two required subunits (β₂ and α₂) involving multiple PCET steps and the conserved tyrosine triad [Y₃₅₆(β₂)–Y₇₃₁(α₂)–Y₇₃₀(α₂)]. We report the synthesis of an active photochemical RNR (photoRNR) complex in which a Re(i)-tricarbonyl phenanthroline ([Re]) photooxidant is attached site-specifically to the Cys in the Y₃₅₆C-(β₂) subunit and an ionizable, 2,3,5-trifluorotyrosine (2,3,5-F₃Y) is incorporated in place of Y₇₃₁ in α₂. This intersubunit PCET pathway is investigated by ns laser spectroscopy on [Re₃₅₆]-β₂:2,3,5-F₃Y₇₃₁-α₂ in the presence of substrate, CDP, and effector, ATP. This experiment has allowed analysis of the photoinjection of a radical into α₂ from β₂ in the absence of the interfacial Y₃₅₆ residue. The system is competent for light-dependent substrate turnover. Time-resolved emission experiments reveal an intimate dependence of the rate of radical injection on the protonation state at position Y₇₃₁(α₂), which in turn highlights the importance of a well-coordinated proton exit channel involving the key residues, Y₃₅₆ and Y₇₃₁, at the subunit interface.     

Single quantum dot (QD) imaging of fluid flow near surfaces

We introduce the use of quantum dot (QD) nanoparticles for near-surface velocimetry and provide preliminary data to demonstrate its feasibility. Evanescent wave illumination is used to image the motion of water-soluble (CdSe)ZnS QDs with a core size of 6 nm within a region of order 100 nm of a surface . Results are presented for the two in-plane components of the velocity field.     

A supramolecular microfluidic optical chemosensor

A supramolecular microfluidic optical chemosensor (muFOC) has been fabricated. A serpentine channel has been patterned with a sol-gel film that incorporates a cyclodextrin supramolecule modified with a Tb(3+) macrocycle. Bright emission from the Tb(3+) ion is observed upon exposure of the (mu)FOC to biphenyl in aqueous solution. The signal transduction mechanism was elucidated by undertaking steady-state and time-resolved spectroscopic measurements directly on the optical chemosensor patterned within the microfluidic network. The presence of biphenyl in the cyclodextrin receptor site triggers Tb(3+) emission by an absorption-energy transfer-emission process. These results demonstrate that the intricate signal transduction mechanisms of supramolecular optical chemosensors are successfully preserved in microfluidic environments.     

Long-range magnetic ordering in iron jarosites prepared by redox-based hydrothermal methods

The iron jarosites, plumbojarosite, Pb0.5Fe3(OH)6(SO4)2, argentojarosite, AgFe3(OH)6(SO4)2, and thallium jarosite, TlFe3(OH)6(SO4)2, along with the selenate-capped jarosite analogues of potassium, KFe3(OH)6(SeO4)2, and rubidium, RbFe3(OH)6(SeO4)2, have been prepared in their analytically pure forms by employing redox-based hydrothermal methods. The crystal structures of these materials have been determined, and all are found to be essentially isostructrual including Pb0.5Fe3(OH)6(SO4)2, which is distinct from the structure reported for naturally mined samples. All iron jarosites show long-range order (LRO), signified by a sharp transition temperature, T(N), which falls in the narrow temperature range of 61.4 +/- 5 K. The mechanism responsible for this ordering has been established by examining magnetostructural correlations for the jarosites possessing various interlayer cation and capping groups. We show that all magnetic properties of jarosites, including LRO, find their origin in the basic magnetic unit, the intralayer Fe3(mu-OH)3 triangle. Field-dependent magnetization experiments are consistent with the antiferromagnetic stacking of an out of plane moment developed from spin canting within Fe3(mu-OH)3 triangles. Together with the previously reported AFe3(OH)6(SO4)2 (A = Na+, K+, Rb+ and NH4+) jarosites, these compounds provide a framework for probing magnetic ordering in a spin frustrated lattice of the largest series of isoelectronic and isostructural kagomé systems yet discovered.     

Proton-directed redox control of O-O bond activation by heme hydroperoxidase models

Hangman metalloporphyrin complexes poise an acid-base group over a redox-active metal center and in doing so allow the "pull" effect of the secondary coordination environment of the heme cofactor of hydroperoxidase enzymes to be modeled. Stopped-flow investigations have been performed to decipher the influence of a proton-donor group on O-O bond activation. Low-temperature reactions of tetramesitylporphyrin (TMP) and Hangman iron complexes containing acid (HPX-CO2H) and methyl ester (HPX-CO2Me) functional groups with peroxyacids generate high-valent Fe=O active sites. Reactions of peroxyacids with (TMP)FeIII(OH) and methyl ester Hangman (HPX-CO2Me)FeIII(OH) give both O-O heterolysis and homolysis products, Compound I (Cpd I) and Compound II (Cpd II), respectively. However, only the former is observed when the hanging group is the acid, (HPX-CO2H)FeIII(OH), because odd-electron homolytic O-O bond cleavage is inhibited. This proton-controlled, 2e- (heterolysis) vs 1e- (homolysis) redox specificity sheds light on the exceptional catalytic performance of the Hangman metalloporphyrin complexes and provides tangible benchmarks for using proton-coupled multielectron reactions to catalyze O-O bond-breaking and bond-making reactions.     

Electron transfer reactions of fluorotyrosyl radicals

The complex Re(bpy)(CO)3CN is an excited state oxidant of tyrosine upon deprotonation of the tyrosyl phenol. A series of Re(bpy-FnY)(CO)3CN complexes ([Re]-FnY: [Re]-Y, [Re]-3-FY, [Re]-3,5-F2Y, [Re]-2,3-F2Y, [Re]-2,3,5-F3Y, [Re]-2,3,6-F3Y, and [Re]-F4Y) have been prepared so as to vary the FnY*/FnY- reduction potential and thus the driving force for electron transfer in this system. Time-resolved emission and nanosecond absorption spectroscopies have been used to measure the rates for charge separation, CS, and charge recombination, CR, for each complex. A driving force analysis reveals that CS is well described by Marcus' theory for ET, is strongly driving force dependent (activated), and occurs in the normal region for ET. CR, on the other hand, is weakly driving force dependent (near activationless) and occurs in the inverted region for ET. These data demonstrate that fluorotyrosines will be powerful probes for unraveling charge transport mechanisms in enzymes that utilize tyrosyl radicals.     

Electron transfer driven by proton fluctuations in a hydrogen-bonded donor-acceptor assembly

The temperature-isotope dependence of proton-coupled electron transfer (PCET) for a noncovalent molecular dyad is reported. The system consists of an excited-state Zn(II) porphyrin that transfers an electron to a naphthalene diimide acceptor through an amidinium-carboxylate interface. Two different isotope effects are observed for variant temperature regimes. A reverse isotope effect (i.e., kH/kD < 1) is observed as T approaches 120 K (kH/kD = 0.9, 120 K), whereas a normal isotope effect (i.e., kH/kD > 1) is recovered as the temperature is increased (kH/kD = 1.2, 300 K). The transition between these limits is smooth, with a crossover temperature of T approximately 160 K. These observations are in accordance with charge-transfer dynamics that are susceptible to bath-induced fluctuations in the proton coordinate.     

Water addition to a two-electron mixed-valence bimetallic center

Water adds to the two-electron mixed-valence Ir(0,II)(2) core of Ir(2)(tfepma)(3)Cl(2)(tfepma = MeN[P(OCH(2)CF(3))(2)](2)) to cleanly generate an Ir(I,III)(2) hydride. Dehydrohalogenation across the Ir-Ir bond returns the complex to an Ir(0,II)(2) species.