Development of a ReaxFF description for gold

Atomistic simulations of the chemistry of thiol-gold-systems have been restricted by the lack of interatomic interaction models for the involved elements. The ReaxFF framework already has potentials for hydrocarbons, making it an attractive basis for extending to the complete AuSCH-system. Here, an interatomic potential for gold, based on the ReaxFF framework, is presented and compared to existing gold potentials available in the literature. Electronic supplementary material  Supplementary Online Material     

Light-ion-induced reactions in mass measurements of neutron-deficient nuclides close to A = 100

A survey of neutron-deficient nuclides which can be produced via proton- and ³He -induced fusion-evaporation reactions in the A = 100 region was made using a Penning trap as a high-resolution mass filter. A comparison of the measured isotopic rates with a statistical model calculation for the proton-induced reactions shows the importance of using the precise binding energy values for the final reaction products. In particular, proton separation energies were found to play an important role in the evaporation process. In addition, accurate masses of 12 nuclides, ^{97-99, 101}Pd , ¹⁰⁰Ag , ^101-105Cd and ^{102, 104}In , were determined with uncertainties of less than 10keV.     

Quaternization of Vinyl/Alkynyl Pyridine Enables Ultrafast Cysteine‐Selective Protein Modification and Charge Modulation

Quaternized vinyl‐ and alkynyl‐pyridine reagents were shown to react in an ultrafast and selective manner with several cysteine‐tagged proteins at near‐stoichiometric quantities. We have demonstrated that this method can effectively create a homogenous antibody–drug conjugate that features a precise drug‐to‐antibody ratio of 2, which was stable in human plasma and retained its specificity towards Her2+ cells. Finally, the developed warhead introduces a +1 charge to the overall net charge of the protein, which enabled us to show that the electrophoretic mobility of the protein may be tuned through the simple attachment of a quaternized vinyl pyridinium reagent at the cysteine residues. We anticipate the generalized use of quaternized vinyl‐ and alkynyl‐pyridine reagents not only for bioconjugation, but also as warheads for covalent inhibition and as tools to profile cysteine reactivity.     

First precision mass measurements of refractory fission fragments

Atomic masses of 95-100Sr, 98-105Zr, and [corrected] 102-110Mo and have been measured with a precision of 10 keV employing a Penning trap setup at the IGISOL facility. Masses of 104,105Zr and 109,110Mo are measured for the first time. Our improved results indicate significant deviations from the previously published values deduced from beta end point measurements. The most neutron-rich studied isotopes are found to be significantly less bound (1 MeV) compared to the 2003 atomic mass evaluation. A strong correlation between nuclear deformation and the binding energy is observed in the two-neutron separation energy in all studied isotope chains.     

Precise atomic masses of neutron-rich Br and Rb nuclei close to the r-process path

The Penning trap mass spectrometer JYFLTRAP, coupled to the Ion-Guide Isotope Separator On-Line (IGISOL) facility at Jyv?skyl?, was employed to measure the atomic masses of neutron-rich ^85-92Br and ^94-97Rb isotopes with a typical accuracy less than 10keV. Discrepancies with the older data are discussed. Comparison to different mass models is presented. Details of nuclear structure, shell and subshell closures are investigated by studying the two-neutron separation energy and the shell gap energy.     

Alkali Metal- and Ammonium Picrate Extraction and Complex Forming Capabilities of d-Glucose and d-Mannose-based Lariat Ethers

The alkali metal- and ammonium picrate extracting ability of d-glucose- and d-mannose-based 15-crown-5 ethers and related lariat ethers was investigated in dichloromethane – water system. A heteroatom was waried in the crown ether containing a 4,6-O-benzylidene-α-d-glucopyranoside unit 6, (X=O), 2 (X=S) and 8a (X=NH). Extracting ability of the latter species (8a) was excellent (97–99%) in regard of all cations (Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺ and NH₄⁺) examined, it was not, howewer, selective. Introduction of a side arm on the nitrogen atom of 8a decreased the extracting ability, but increased the selectivity. In this series of compounds (8b–f, 4), 4 with a pyridylethyl substituent allowed the extraction of sodium picrate in 72%. The glucose-based macrocycles 8a, 8e and 8f formed a stronger complex with the cations examined than the mannose-based analogues 9a, 9e and 9f, that can be explained by the all-gauche conformation of the former ones. It was pointed out that in the case of crowns with tertiary amine moieties, the basicity increases the quantity of the picrates extracted. According to complex forming measurements by FAB-MS, the best sodium ion selectivity was achieved by the γ-hydroxypropyl substituted lariat ether (8e). Possible structures of the complexes formed by the two types of monosacharides with sodium cation were evaluated by molecule modelling calculations.     

Synthesis of Lanthanide(III) Chelates by Using ‘Click’ Chemistry

The copper(I)‐catalyzed dipolar [2+3] cycloaddition reaction of an azide and a terminal alkyne is exploited in the preparation of various europium(III), terbium(III), and dysprosium(III) chelates (Schemes 1–3). By changing the nature of the alkyne and the azide, a wide range of chelates and biomolecule‐labeling reactants were obtained. The photophysical properties (Table) of the synthesized chelates are also discussed.     

Mass spectrometric studies of benzoxazine resorcarenes

Eleven differently substituted 3,4-dihydro-2H-1,3-benzoxazine resorcarenes were studied by electrospray ionisation (ESI) and matrix-assisted laser desorption/ionisation (MALDI) mass spectrometry, using Fourier transform ion cyclotron resonance (FT-ICR) and time-of-flight (TOF) mass spectrometers, respectively. Under ESI conditions it was possible to transfer the intact resorcarenes from solution to the gas phase, yielding [M + H](+) and [M + 2H](+) ions as the main ions observed. Energy increase of the ions induced ready decomposition through successive eliminations of four CH(2)NR groups. Ion-molecule reactions showed that the ionising proton was situated somewhere inside the molecule and could not be reached with neutral reagent gases. In the host-guest complexation experiments, the benzoxazine resorcarenes studied turned out to be poor hosts for alkali metal and ammonium ions. In MALDI experiments, 2,5-dihydroxybenzoic acid proved to be the best matrix for these compounds. However, the intensity of the [M + H](+) ions was low for all compounds, and extensive fragmentation with consecutive elimination of CH(2)NR groups was observed.     

Configurational energetics in ice ih probed by compton scattering

Temperature-induced changes in the ground-state electron momentum density of polycrystalline ice Ih are studied with high accuracy by Compton scattering utilizing synchrotron radiation. A unique feasibility of the technique to provide direct experimental information on configurational enthalpies and heat capacities is demonstrated. The configurational enthalpy, obtained with an accuracy of 1.5 meV, evolves linearly with temperature above T=100 K. Consequently the configurational heat capacity is found to be constant, c{p}{config}=(0.44+/-0.11) J g{-1} K-1, in this temperature regime. Obtaining these quantities experimentally is fundamentally important for evaluating the accuracy of molecular-dynamics simulations schemes.     

Precision mass measurements of radioactive nuclei at JYFLTRAP

The Penning trap mass spectrometer JYFLTRAP was used to measure the atomic masses of radioactive nuclei with an uncertainty better than 10 keV. The atomic masses of the neutron-deficient nuclei around the line were measured to improve the understanding of the rp-process path and the SbSnTe cycle. Furthermore, the masses of the neutron-rich gallium ( ) to palladium ( ) nuclei have been measured. The physics impacts on the nuclear structure and the r-process paths are reviewed. A better understanding of the nuclear deformation is presented by studying the pairing energy around .