THE EFFECT OF PERIPHERAL SUBSTITUTION ON THE BATHOCHROMIC SHIFT OF THE Qy TRANSITION OF BACTERIOCHLOROPHYLL DIMERS; in vitro MODELS OF THE PROTEIN EFFECT ON THE SPECTRUM OF PIGMENT CENTERS IN THE LIGHT-HARVESTING COMPLEXES*

Abstract— The effect of chemical modifications in the side groups of the isocyclic ring V on the formation, optical absorption and circular dichroism of bacteriochlorophyll (Bchl) dimers was examined in a mixture of formamide and water containing TritonX–100 and variable amounts of pyridine. Substitution of the carbomethoxy group in the C13² position with a hydrogen atom, had no effect on the dimerization constant but increased the shift of the Q_y transition by 1000 cm^-1 with respect to the native Bchl. Substitution of the C13 hydrogen atom with OH decreased the shift of the Q_y transition by 400 cm^-1. The similarity between the spectra of the modified Bchl dimers and Bchl dimers in vivo indicates that protein binding to the side groups at Bchl dimers may profoundly affect the energy of their Q_y transition but have minor effects on the Q_y transitions of the monomelic Bchl.     

Bildung von Malondialdehyd bei der Bestrahlung wäßriger Glucoselösungen

The malondialdehyde content of a 1% aqueous glucose solution irradiated in the presence and absence of oxygen and at various pH values has been estimated. From the data obtained a reaction scheme for the formation of malondialdehyde has been proposed.     

Observation of B(s)0-->K+ K- and measurements of branching fractions of charmless two-body decays of B0 and B(s)0 mesons in pp collisions at square root of s = 1.96 TeV

We search for decays of the type B(s)0-->h+ h'- (where h,h' = K or pi) in 180 pb(-1) of pp collisions collected at the Tevatron by the upgraded Collider Detector at Fermilab. We report the first observation of the new mode B(s)0-->K+ K- with a yield of 236+/-32 events, corresponding to (fs/fd) x B(B(s)0-->K+ K-)/B(B0-->K+ pi-) = 0.46+/-0.08stat+/-0.07syst, where fs/fd is the ratio of production fractions of B(s)0 and B0. We find results in agreement with world averages for the B0 modes, and set the following new limits at 90% C.L.: B(B(s)0-->K- pi+) < 5.6 x 10(-6) and B(B(s)0-->pi+ pi-) < 1.7 x 10(-6).     

Measurement of the inclusive jet cross section using the kT algorithm in pp collisions at (square root s)=1.96 TeV

We report on a measurement of the inclusive jet production cross section as a function of the jet transverse momentum in pp collisions at (square root s)=1.96 TeV using data collected with the upgraded Collider Detector at Fermilab in run II, corresponding to an integrated luminosity of 385 pb-1. The measurement is carried out for jets with rapidity 0.1相似文献   

Modulation of fragmental charge transfer via hydrogen bonds. Direct measurement of electronic contributions

Hydrogen bonds play an important role in an overwhelming variety of fields from biology to surface and supramolecular chemistry. The term "hydrogen bond" refers to a wide range of interactions with various covalent and polar contributions. In particular, hydrogen bonds have an important role in the folding and packing of peptides and nucleic acids. Recent studies also point to the importance of hydrogen bonding in the context of second-shell interactions, in metal binding and selectivity in metalloproteins, and in controlling the dynamics of membrane proteins. In this study, we demonstrate and quantify the modulation of fragmental charge transfer from hydrogen-bonded ligands to a metal center, by employing our recently introduced molecular potentiometer. The molecular details that affect this type of fragmental charge transfer are presented and a path for transferring chemical information is demonstrated. We found that H-bond interactions in the extended positions of axial ligands provide an effective means of modulating the amount of fragmental charge transfer to a metal center, thereby dramatically influencing the electronic properties of the ligand, the binding affinity, and the binding of additional ligands. The magnitude of fragmental charge-transfer modulation induced by a single ligand-solvent H-bond interaction is comparable to those induced by covalent substitution, although H-bond enthalpy is only on the order of several kilojoules per mole. Importantly, we find a significant change in the ligand electronic properties, even for weak C-H...O=C H-bond formation, where the bond enthalpy is substantially lower than for conventional H-bond interactions. The excess fragmental charge transferred to the metal center, deduced from the spectroscopic measurements, correlates well with the computationally determined values. Our findings underscore the importance of second-shell interactions in the active sites of enzymes, beyond the structural and electrostatic importance that is widely recognized today.     

Distances between classes in $$W^{1,1}(\Omega ;{\mathbb {S}}^{1})$$

We introduce an equivalence relation on the space \(W^{1,1}(\Omega ;{\mathbb {S}}^1)\) which classifies maps according to their “topological singularities”. We establish sharp bounds for the distances (in the usual sense and in the Hausdorff sense) between the equivalence classes. Similar questions are examined for the space \(W^{1,p}(\Omega ;{\mathbb {S}}^1)\) when \(p>1\).     

Measurement of the Bs0-Bs0 oscillation frequency

We present the first precise measurement of the Bs0-Bs0 oscillation frequency Deltams. We use 1 fb-1 of data from pp collisions at sqrts=1.96 TeV collected with the CDF II detector at the Fermilab Tevatron. The sample contains signals of 3600 fully reconstructed hadronic Bs decays and 37,000 partially reconstructed semileptonic Bs decays. We measure the probability as a function of proper decay time that the Bs decays with the same, or opposite, flavor as the flavor at production, and we find a signal consistent with Bs0-Bs0 oscillations. The probability that random fluctuations could produce a comparable signal is 0.2%. Under the hypothesis that the signal is due to Bs0-Bs0 oscillations, we measure Deltams=17.31(-0.18)+0.33(stat)+/-0.07(syst) ps-1 and determine |Vtd/Vts|=0.208(-0.002)+0.001(expt)-0.006(+0.008)(theor).