Direct and β-delayed multi-proton emission from atomic nuclei with a time projection chamber: the cases of 43Cr, 45Fe, and 51Ni

The two-proton radioactivity of ⁴⁵Fe was studied experimentally with a time projection chamber. The aim of the experiment was the reconstruction of the proton tracks in three dimensions. Energy and angular correlations have been determined and the data are compared with theoretical models, in particular with a three-body model. Moreover, the decay of ⁴³Cr was studied and ??-delayed one-, two- and three-proton emission could be established. The correlations observed for ??-delayed two-proton emission favour a sequential emission. Finally, ??-delayed two-proton emission was observed for the first time for ⁵¹Ni.     

On the relative roles of higher-order nonlinearity and ionization in ultrafast light-matter interactions

Far off-resonant ultrafast and nonlinear light-matter interactions are studied using a one-dimensional atomic model. Results from a pump-probe diagnostic reveal that any higher-order nonlinear refraction is masked by ionization-induced defocusing before it becomes significant. On the other hand, we show that signatures of a higher-order nonlinearity may still be manifest via low-order harmonics of the pump center frequency. Implications for filamentation of femtosecond pulses are pointed out.     

Porous three-dimensional nanorod arrays through selective chemical etching of nanocomposites

Three-dimensional Cu-Si and Cu-SiO(2) nanorod arrays containing ~68 at% Cu have been fabricated by a glancing angle co-deposition technique. By selectively etching Cu in 0.05 M KCN methanol solution, porous nanorods with different shapes form, which are promising for applications in sensors, catalysts, and as medical capsules that are able to be loaded with functional materials.     

Nonclassical oxygen atom transfer reactions of oxomolybdenum(VI) bis(catecholate)

Mechanistic studies indicate that the oxomolybdenum(vi) bis(3,5-di-tert-butylcatecholate) fragment deoxygenates pyridine-N-oxides in a reaction where the oxygen is delivered to molybdenum but the electrons for substrate reduction are drawn from the bound catecholate ligands, forming 3,5-di-tert-butyl-1,2-benzoquinone.     

Triplex-directed covalent cross-linking of a DNA nanostructure

The triplex approach to DNA recognition is exploited to direct covalent inter-strand cross-links to unique locations within a pre-assembled DNA nanostructure. This approach can be used to improve the stability of DNA nanostructures and demonstrates the feasibility of directing other reactive groups to unique locations within these complexes.     

Probing the functional limits of the norepinephrine transporter with self-reporting, fluorescent stilbazolium dimers

A series of stilbazolium dimers were synthesized and investigated as sterically demanding ligands targeting the norepinephrine transporter (NET). The environmentally sensitive fluorescence of the dyes enables their use as self-reporting ligands; binding to and displacement from NET can be monitored by fluorescence microscopy.     

Spectral line parameters including temperature dependences of self- and air-broadening in the 2←0 band of CO at 2.3 μm

Temperature dependences of pressure-broadened half-width and pressure-induced shift coefficients along with accurate positions and intensities have been determined for transitions in the 2←0 band of ¹²C¹⁶O from analyzing high-resolution and high signal-to-noise spectra recorded with two different Fourier transform spectrometers. A total of 28 spectra, 16 self-broadened and 12 air-broadened, recorded using high-purity (≥99.5% ¹²C-enriched) CO samples and CO diluted with dry air (research grade) at different temperatures and pressures, were analyzed simultaneously to maximize the accuracy of the retrieved parameters. The sample temperatures ranged from 150 to 298 K and the total pressures varied between 5 and 700 Torr. A multispectrum nonlinear least squares spectrum fitting technique was used to adjust the rovibrational constants (G, B, D, etc.) and intensity parameters (including Herman–Wallis coefficients), rather than determining individual line positions and intensities. Self- and air-broadened Lorentz half-width coefficients, their temperature dependence exponents, self- and air-pressure-induced shift coefficients, their temperature dependences, self- and air- line mixing coefficients, their temperature dependences and speed dependence have been retrieved from the analysis. Speed-dependent line shapes with line mixing employing off-diagonal relaxation matrix element formalism were needed to minimize the fit residuals. This study presents a precise and complete set of spectral line parameters that consistently reproduce the spectrum of carbon monoxide over terrestrial atmospheric conditions.     

Molybdenum(VI) complexes of a 2,2'-biphenyl-bridged bis(amidophenoxide): competition between metal-ligand and metal-amidophenoxide π bonding

The 2,2'-biphenyl-bridged bis(2-aminophenol) ligand 4,4'-di-tert-butyl-N,N'-bis(3,5-di-tert-butyl-2-hydroxyphenyl)-2,2'-diaminobiphenyl ((t)BuClipH(4)) reacts with MoO(2)(acac)(2) to form ((t)BuClipH(2))MoO(2), where the diarylamines remain protonated and bind trans to the terminal oxo groups. This complex readily loses water on treatment with pyridine or 3,5-lutidine to form mono-oxo complexes ((t)BuClip)MoO(L), which exhibit predominantly a cis-β geometry with an aryloxide trans to the oxo group. Exchange of the pyridine ligands is rapid and takes place by a dissociative mechanism, which occurs with retention of stereochemistry at molybdenum. Oxo-free alkoxide complexes ((t)BuClip)Mo(OR)(2) are formed from ((t)BuClipH(2))MoO(2) and ROH. Treatment of NMo(O(t)Bu)(3) with (t)BuClipH(4) results in complete deprotonation of the bis(aminophenol) and formation of a dimolybdenum complex ((t)BuClip)Mo(μ-N)(μ-NH(2))Mo((t)BuClip) containing both a bridging nitride (Mo-N = 1.848 ?, Mo-N-Mo = 109.49°) and a bridging amide group. The strong π bonding of this bis(amidophenoxide) ligand allows the molybdenum center to interconvert readily among species forming three, two, one, or zero π bonds from multiply bonded ligands.     

Cu(II)-promoted methanolysis of N,N-dipicolylacetamide. multistep activation by decoupling of > ̈̈N-C═O resonance via Cu(II)-N binding, delivery of the Cu(II):((-)OCH3) nucleophile, and metal ion assistance of the departure of the leaving group

The methanolysis of the Cu(II) complex of N-acetyl-N,N-bis(2-picolyl)amine (2) was investigated by a kinetic study as a function of pH in methanol at 25 °C and computationally by DFT calculations. The active species is the basic form of the complex (3(-)), or (1:Cu(II))((-)OCH(3))(HOCH(3))), and the rate constant for its solvolysis is k(max) = 1.5 × 10(-4) s(-1). The mechanism involves Cu(II) binding to the amide N lone pair, decoupling it from >N-C═O resonance, concomitant with Cu(II):((-)OCH(3)) delivery to the adjacent >N-C═O unit, followed by Cu(II)-assisted departure of the N,N-bis(2-picolyl)amide from a tetrahedral intermediate.