Fine structure in proton emission from 145Tm discovered with digital signal processing

Fine structure in proton emission from the 3.1(3) mus activity of 145Tm was discovered by using a novel technique of digital processing of overlapping recoil implantation and decay signals. Proton transitions to the ground state of 144Er and to its first excited 2(+) state at 0.33(1) MeV with a branching ratio I(p)(2(+))=9.6+/-1.5% were observed. The structure of the 145Tm wave function and the emission process were analyzed by using particle-core vibration coupling models.     

Probing the different stages in contacting a single molecular wire

A crucial problem in molecular electronics is the control of the electronic contact between a molecule and its electrodes. As a model system, we investigated the contact between the molecular wire group of a C90H98 (Lander) molecule and the edge of a Cu(111) monatomic step. The reproducible contact and decontact of the wire was obtained by manipulating the Lander with a low temperature scanning tunneling microscope. The electronic standing wave patterns on the Cu(111) surface serve to monitor the local electronic perturbation caused by the interaction of the wire end with the step edge, giving information on the quality of the contact.     

Probing the negative Wigner function of a pulsed single photon point by point

We investigate quantum properties of pulsed light fields point by point in phase space. We probe the negative region of the Wigner function of a single photon generated by the means of waveguided parametric down conversion. This capability is achieved by employing loss-tolerant photon-number resolving detection, allowing us to directly observe the oscillations of the photon statistics in dependence of applied displacements in phase space. Our scheme is highly mode sensitive and can reveal the single-mode character of the signal state.     

A Lewis Acid-Catalyzed Procedure for the Conversion of 2-Methoxyethoxymethyl Ethers to Carboxylic Esters

A procedure for the conversion of 2-methoxy-ethoxymethyl (MEM) ethers to carboxylic esters employed ferric chloride (0.4 equivalents) and a carboxylic anhydride (14 equivalents) and exhibited selectivity for the MEM ether functionality in the presence of benzyl ethers.     

Radical Reactivity of the Biradical [⋅P(μ-NTer)2P⋅] and Isolation of a Persistent Phosphorus-Cantered Monoradical [⋅P(μ-NTer)2P-Et]

The activation of C−Br bonds in various bromoalkanes by the biradical [⋅P(μ-NTer)₂P⋅] ( 1 ) (Ter=2,6-bis-(2,4,6-trimethylphenyl)-phenyl) is reported, yielding trans-addition products of the type [Br−P(μ-NTer)₂P−R] ( 2 ), so-called 1,3-substituted cyclo-1,3-diphospha-2,4-diazanes. This addition reaction, which represents a new easy approach to asymmetrically substituted cyclo-1,3-diphospha-2,4-diazanes, was investigated mechanistically by different spectroscopic methods (NMR, EPR, IR, Raman); the results suggested a stepwise radical reaction mechanism, as evidenced by the in-situ detection of the phosphorus-centered monoradical [⋅P(μ-NTer)₂P-R].< To provide further evidence for the radical mechanism, [⋅P(μ-NTer)₂P-Et] ( 3Et ⋅) was synthesized directly by reduction of the bromoethane addition product [Br-P(μ-NTer)₂P-Et] ( 2 a ) with magnesium, resulting in the formation of the persistent phosphorus-centered monoradical [⋅P(μ-NTer)₂P-Et], which could be isolated and fully characterized, including single-crystal X-ray diffraction. Comparison of the EPR spectrum of the radical intermediate in the addition reaction with that of the synthesized new [⋅P(μ-NTer)₂P-Et] radical clearly proves the existence of radicals over the course of the reaction of biradical [⋅P(μ-NTer)₂P⋅] ( 1 ) with bromoethane. Extensive DFT and coupled cluster calculations corroborate the experimental data for a radical mechanism in the reaction of biradical [⋅P(μ-NTer)₂P⋅] with EtBr. In the field of hetero-cyclobutane-1,3-diyls, the demonstration of a stepwise radical reaction represents a new aspect and closes the gap between P-centered biradicals and P-centered monoradicals in terms of radical reactivity.     

Fast Photochemical Oxidation of Proteins (FPOP) Maps the Epitope of EGFR Binding to Adnectin

Epitope mapping is an important tool for the development of monoclonal antibodies, mAbs, as therapeutic drugs. Recently, a class of therapeutic mAb alternatives, adnectins, has been developed as targeted biologics. They are derived from the 10th type III domain of human fibronectin (¹⁰Fn3). A common approach to map the epitope binding of these therapeutic proteins to their binding partners is X-ray crystallography. Although the crystal structure is known for Adnectin 1 binding to human epidermal growth factor receptor (EGFR), we seek to determine complementary binding in solution and to test the efficacy of footprinting for this purpose. As a relatively new tool in structural biology and complementary to X-ray crystallography, protein footprinting coupled with mass spectrometry is promising for protein–protein interaction studies. We report here the use of fast photochemical oxidation of proteins (FPOP) coupled with MS to map the epitope of EGFR-Adnectin 1 at both the peptide and amino-acid residue levels. The data correlate well with the previously determined epitopes from the crystal structure and are consistent with HDX MS data, which are presented in an accompanying paper. The FPOP-determined binding interface involves various amino-acid and peptide regions near the N terminus of EGFR. The outcome adds credibility to oxidative labeling by FPOP for epitope mapping and motivates more applications in the therapeutic protein area as a stand-alone method or in conjunction with X-ray crystallography, NMR, site-directed mutagenesis, and other orthogonal methods. Figure

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