Design of Turn‐On Near‐Infrared Fluorescent Probes for Highly Sensitive and Selective Monitoring of Biopolymers

Simple, sensitive, and selective detection of specific biopolymers is critical in a broad range of biomedical and technological areas. We present a design of turn‐on near‐infrared (NIR) fluorescent probes with intrinsically high signal‐to‐background ratio. The fluorescent signal generation mechanism is based on the aggregation/de‐aggregation of phthalocyanine chromophores controlled by selective binding of small‐molecule “anchor” groups to a specific binding site of a target biopolymer. As a proof‐of‐concept, we demonstrate a design of a sensor for EGFR tyrosine kinase—an important target in cancer research. The universality of the fluorescent signal generation mechanism, as well as the dependence of the response selectivity on the choice of the small‐molecule “anchor” group, make it possible to use this approach to design reliable turn‐on NIR fluorescent sensors for detecting specific protein targets present in the low‐nanomolar concentration range.     

The spatial resolution of the CMS ME1/1 muon station cathode strip chambers with CRAFT08 data

The spatial resolution of the outer part of the ME1/1 muon station has been studied with CRAFT08 (Cosmic Rays At Four Tesla-2008) data at the CMS detector (CERN). The ME1/1 Cathode Strip Chamber (CSC) layer spatial resolution as a function of the CMS solenoid magnetic field is presented. The influence of the strip width and anode wire tilt on the spatial resolution has been studied. Finally, the spatial resolution for the ME1/1 6-layer CSC was calculated and the ME1/1 outer part spatial resolution was estimated.     

Group 3 and 4 single-site catalysts for stereospecific polymerization of styrene

The present review aims at a comprehensive survey of controlled stereospecific styrene polymerization by single-site catalysts to give syndiotactic and isotactic polystyrene. The early transition metals (groups 3 and 4) complexes that were successfully applied as catalyst precursors are reviewed. Catalytic performances and mechanistic insights, in particular in the stereoregulation phenomenon, are discussed.     

Retrieval of aerosol optical depth in vicinity of broken clouds from reflectance ratios: Sensitivity study

We conducted a sensitivity study to better understand the potential of a new method for retrieving aerosol optical depth (AOD) under partly cloudy conditions. This method exploits ratios of reflectances in the visible spectral range and provides an effective way to avoid three-dimensional (3D) cloud effects. The sensitivity study is performed for different observational conditions and random errors in input data. The results of the sensitivity study suggest that this ratio method has the ability to detect clear pixels even in close proximity to clouds. Such detection does not require a statistical analysis of the two-dimensional (2D) horizontal distribution of reflected solar radiation, which makes it suitable for operational retrievals. In comparison with previously suggested approaches, the ratio method has the capability to increase the “harvest” of clear pixels. Similar to the traditional independent pixel approximation (IPA), the ratio method has a low computational cost for retrieving AOD. In contrast to the IPA method, the ratio method provides much more accurate estimations of the AOD values under broken cloud conditions: pixel-based and domain-averaged estimations of errors in AOD are about 25% and 10%, respectively. Finally, both the ratio-based cloud screening and the accuracy of domain-averaged ratio-based AOD values do not suffer greatly when 5% random errors are introduced in the reflectances.     

ESEEM studies of peptide nitrogen hyperfine coupling in tyrosyl radicals and model peptides

Tyrosyl radicals are important in long-range electron transfer in several enzymes, but the protein environmental factors that control midpoint potential and electron transfer rate are not well understood. To develop a more detailed understanding of the effect of protein sequence, we have performed 14N and 15N electron spin echo envelope modulation (ESEEM) measurements on tyrosyl radical, generated either in polycrystalline tyrosinate or in its 15N-labeled isotopomer, by UV photolysis. 14N-ESEEM was also performed on tyrosyl radical generated in tyrosine-containing pentapeptide samples. Simulation of the 14N- and 15N-tyrosyl radical ESEEM measurements yielded no significant isotropic hyperfine splitting to the amine or amide nitrogen; the amplitude of the anisotropic, nitrogen hyperfine coupling (0.21 MHz) was consistent with a dipole-dipole distance of 3.0 A. Density functional theory was used to calculate the isotropic and anisotropic hyperfine couplings to the amino nitrogen in four different tyrosyl radical conformers. Comparison with the simulated data suggested that the lowest energy radical conformer, generated in tyrosine at pH 11, has a 76 degrees Calpha-Cbeta-C1'-C2' ring and a -73 degrees C-Calpha-Cbeta-C1' backbone dihedral angle. In addition, the magnitude, orientation, and asymmetry of the nuclear quadrupole coupling tensor were derived from analysis of the tyrosyl radical 14N-ESEEM. The simulations showed differences in the coupling and orientation of the nuclear quadrupole tensor, when the tyrosinate and pentapeptide samples were compared. These results suggest sequence- or conformation-induced changes in the ionic character of the NH bond in different tyrosine-containing peptides.     

Effect of surrounding point charges on the density functional calculations of NixOx clusters (x = 4-12)

Embedded Ni(x)O(x) clusters (x = 4-12) have been studied by the density-functional method using compensating point charges of variable magnitude to calculate the ionic charge, bulk modulus, and lattice binding energy. The computations were found to be strongly dependent on the value of the surrounding point charge array and an optimum value could be found by choosing the point charge to reproduce the experimentally observed Ni--O lattice parameter. This simple, empirical method yields a good match between computed and experimental data, and even small variation from the optimum point charge value produces significant deviation between computed and measured bulk physical parameters. The optimum point charge value depends on the cluster size, but in all cases is significantly less than +/-2.0, the formal oxidation state typically employed in cluster modeling of NiO bulk and surface properties. The electronic structure calculated with the optimized point charge magnitude is in general agreement with literature photoemission and XPS data and agrees with the presently accepted picture of the valence band as containing charge-transfer insulator characteristics. The orbital population near the Fermi level does not depend on the cluster size and is characterized by hybridized Ni 3d and O 2p orbitals with relative oxygen contribution of about 70%.     

Adaptive control for discrete-time Markov processes with unbounded costs: Average criterion

The paper deals with a class of discrete-time Markov control processes with Borel state and action spaces, and possibly unbounded one-stage costs. The processes are given by recurrent equations x _{t +1}=F(x _t ,a _t ,ξ _t ), t=1,2,… with i.i.d. ℜ ^k – valued random vectors ξ _t whose density ρ is unknown. Assuming observability of ξ _t , and taking advantage of the procedure of statistical estimation of ρ used in a previous work by authors, we construct an average cost optimal adaptive policy. Received March/Revised version October 1997