Isolation and Hydrogenation of a Complex with a Terminal Iridium–Nitrido Bond

An N for Ir : The synthesis and X‐ray crystal structure of a late‐transition‐metal complex with a terminal nitrido ligand and its hydrogenation to the related amido complex are reported (see scheme).

     

Hyperspectral NIR imaging for calibration and prediction: a comparison between image and spectrometer data for studying organic and biological samples

A hyperspectral image in the near infrared contains thousands of position-referenced spectra. After imaging reference materials of known composition it is possible to build Partial Least Squares (PLS) regression models for predicting unknown compositions from new images or spectra. In this paper a comparison is made between spectra from a hyperspectral image and spectra from two spectrometers: a scanning grating instrument with rotating sample holders and an FT-NIR instrument utilizing a fiber-optic probe. The raw spectra and the quality of the PLS calibration models and predictions are compared. Two sample datasets consist of a set of 13 designed artificial mixtures of pure constituents and a selection of 13 sampled cheeses. The prediction error from the hyperspectral image spectra is between that of the two spectrometers. For a typical food sample, the average bias [and replicate standard deviation] was -0.6% [0.5%] for protein and -0.2% [1.3%] for fat. Comparable values for the best spectrometer were -0.2% bias for protein and -0.5% for fat. Some of the advantages of working with hyperspectral images are highlighted: the simultaneous exploration of representations of both spectral and spatial data, and the analysis of concentration profiles and concentration maps all contribute to better characterization of organic and biological materials.     

Cosmic-Ray Modulation: an Ab Initio Approach

A better understanding of cosmic-ray modulation in the heliosphere can only be gained through a proper understanding of the effects of turbulence on the diffusion and drift of cosmic rays. We present an ab initio model for cosmic-ray modulation, incorporating for the first time the results yielded by a two-component turbulence transport model. This model is solved for periods of minimum solar activity, utilizing boundary values chosen so that model results are in fair to good agreement with spacecraft observations of turbulence quantities, not only in the solar ecliptic plane but also along the out-of-ecliptic trajectory of the Ulysses spacecraft. These results are employed as inputs for modelled slab and 2D turbulence energy spectra. The latter spectrum is chosen based on physical considerations, with a drop-off at the very lowest wavenumbers commencing at the 2D outerscale. There currently exist no models or observations for this quantity, and it is the only free parameter in this study. The modelled turbulence spectra are used as inputs for parallel mean free path expressions based on those derived from quasi-linear theory and perpendicular mean free paths from extended nonlinear guiding center theory. Furthermore, the effects of turbulence on cosmic-ray drifts are modelled in a self-consistent way, employing a recently developed model for drift along the wavy current sheet. The resulting diffusion coefficients and drift expressions are applied to the study of galactic cosmic-ray protons and antiprotons using a three-dimensional, steady-state cosmic-ray modulation code, and sample solutions in fair agreement with multiple spacecraft observations are presented.     

HMSC: simultaneously detected heteronuclear shift correlation through multiple and single bonds

A new 2D pulse sequence HMSC (heteronuclear multiple-bond and single-bond coupling connectivities) for the simultaneous detection of long-range and one-bond heteronuclear connectivities is proposed which allows the two types of responses to be separated and the corresponding (n)J(CH) and (1)J(CH) connectivity maps to be calculated. (n)J(CH) coherences are selectively labeled in the course of the pulse sequence, the correspondingly acquired data are separately stored, and a simple add/subtract procedure is applied to disentangle and edit (n)J(CH) and (1)J(CH) responses prior to final data processing. Unlike standard methods, which are designed to measure one single type of heteronuclear spin-spin interactions and to efficiently suppress the other, both (n)J(CH) and (1)J(CH) are measured simultaneously in a single experiment with the HMSC pulse sequence. Compared to the common strategy with two standard experiments applied one after the other, e.g., HMBC and HMQC, valuable measuring time may be saved with this single experiment approach. The efficiency of the new pulse sequence and the quality of the corresponding spectra are demonstrated using strychnine. Features such as sensitivity, lineshapes, and the suppression of (1)J(CH) residual peaks in the final (n)J(CH) subspectra are investigated and compared with the corresponding results obtained with standard methods. The attractive and unique single experiment approach, its high efficiency, and its easy experimental setup together with straightforward data processing make HMSC a valuable experimental alternative for the today's more time-consuming "two-step" practice and makes it suitable for standard routine applications.     

Ab initio study of the solvent H-bonding effect on ESIPT reaction and electronic transitions of 3-hydroxychromone derivatives

The electronic transitions occurring in 4-(N,N-dimethylamino)-3-hydroxyflavone (DMAF) and 2-furanyl-3-hydroxychromone (FHC) were investigated using the TDDFT method in aprotic and protic solvents. The solvent effect was incorporated into the calculations via the PCM formalism. The H-bonding between solute and protic solvent was taken into account by considering a molecular complex between these molecules. To examine the effect of the H-bond on the ESIPT reaction, the absorption and emission wavelengths as well as the energies of the different states that intervene during these electronic transitions were calculated in acetonitrile, ethanol and methanol. The calculated positions of the absorption and emission wavelengths in various solvents were in excellent agreement with the experimental spectra, validating our approach. We found that in DMAF, the hydrogen bonding with protic solvents makes the ESIPT reaction energetically unfavourable, which explains the absence of the ESIPT tautomer emission in protic solvents. In contrast, the excited tautomer state of FHC remains energetically favourable in both aprotic and protic solvents. Comparing our calculations with the previously reported time-resolved fluorescence data, the ESIPT reaction of DMAF in aprotic solvents is reversible because the emitting states are energetically close, whereas in FHC, ESIPT is irreversible because the tautomer state is below the corresponding normal state. Therefore, the ESIPT reaction in DMAF is controlled by the relative energies of the excited states (thermodynamic control), while in FHC the ESIPT is controlled probably by the energetic barrier (kinetic control).     

Bonding situation and N-O-bond strengths in amine-N-oxides--a combined experimental and theoretical study

The bonding situation and energetics of the N-O bond in a series of amine-N-oxides, Ph(x)(CH(3))(3-x)N-O, where x = 0-3, were analyzed experimentally and theoretically. There is a notable nearly linear decrease of the N-O bond dissociation energies (BDEs) for this series with an increasing number of phenyl groups x. This was investigated experimentally by X-ray high angle multipole refinement techniques in combination with subsequent topological analysis of the electron density for the representative (CH(3))(2)PhN-O, 2, and complementary theoretical calculations at the DFT and multireference CASSCF and MR-perturbation theory (MCQDPT2) levels. Both the theoretical and experimental results unambiguously revealed a polar covalent σ-bond for the N-O bond with an essentially identical bonding situation for all amine-N-oxides studied. This apparent disparity between the bonding situation and the trend of BDEs is attributed to the large differences of the relaxation energies of the corresponding amines Ph(x)(CH(3))(3-x)N, (x = 0-3), respectively, the required preparation energies (ΔE(prep)) for the reverse N-O bond forming process. The detailed theoretical analysis of the amines allowed us to trace the trend of larger values of ΔE(prep) for a higher number of phenyl groups x to an increase of n(N) → π*(C-C) delocalization interactions.     

Thermal expansion and Grüneisen parameters of Ba(Fe(1-x)Co(x))2As2: a thermodynamic quest for quantum criticality

Thermal expansion data are used to study the uniaxial pressure dependence of the electronic-magnetic entropy of Ba(Fe(1-x)Co(x))2As2. Uniaxial pressure is found to be proportional to doping and, thus, also an appropriate tuning parameter in this system. Many of the features predicted to occur for a pressure-tuned quantum critical system, in which superconductivity is an emergent phase hiding the critical point, are observed. The electronic-magnetic Grüneisen parameters associated with the spin-density wave and superconducting transitions further demonstrate an intimate connection between both ordering phenomena.     

Phosphopeptide selective coordination complexes as promising SRC homology 2 domain mimetics

Src Homology 2 (SH2) domains are the paradigm of phosphotyrosine (pY) protein recognition modules and mediate numerous cancer-promoting protein-protein complexes. Effective SH2 domain mimicry with pY-binding coordination complexes offers a promising route to new and selective disruptors of pY-mediated protein-protein interactions. We herein report the synthesis and in vitro characterization of a library of coordination complex SH2 domain proteomimetics. Compounds were designed to interact with phosphopeptides via a two-point interaction, principally with pY, and to make secondary interactions with pY+2/3, thereby achieving sequence-selective discrimination. Here, we report that lead mimetics demonstrated high target phosphopeptide affinity (K(a) ～ 10(7) M(-1)) and selectivity. In addition, biological screening in various tumor cells for anticancer effects showed a high degree of variability in cytotoxicity among receptors, which supported the proposed two-point binding mode. Several receptors potently disrupted cancer cell viability in breast cancer, prostate cancer, and acute myeloid leukemia cell lines.     

Host structure dependence of light yield and proportionality in scintillators in terms of hot and thermalized carrier transport

Several outstanding questions, including why complex halide scintillator host structures allow higher light yield and flatter electron energy response than simple monovalent metal halides, have remained unanswered by current models of luminescence in dense ionization tracks. Our measurements of nonlinear quenching kinetic order, recent literature on hot‐electron transport in scintillators, and calculations presented here of hot‐electron velocity from band structure of SrI₂ and NaI, lead us to expand our previously described diffusion and nonlinear quenching model to include hot‐electron transport. Trends in multivalent versus monovalent metal halides, heavier versus lighter halides, and halides versus oxides versus semiconductors can be predicted based on optical phonon frequency, thermalized band edge mobilities, velocity in the upper conduction bands, and hole self‐trapping. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis of α-N-Ethylamino Acids and their Derivatives

 A new synthesis of α-N-ethylamino acids starting from α-amino acids using hexafluoroacetone as protecting and activating agent is described. The hexafluoroacetone-protected N-ethylamino acid derivatives obtained are activated lactons. Therefore, they can be directly transformed without the need of an additional activation step with various nucleophiles into the corresponding carboxylic acid derivatives.