Determination of Uranium Central-Field Covalency with 3d4f Resonant Inelastic X-ray Scattering.

Understanding the nature of metal-ligand bonding is a major challenge in actinide chemistry. We present a new experimental strategy for addressing this challenge using actinide 3d4f resonant inelastic X-ray scattering (RIXS). Through a systematic study of uranium(IV) halide complexes, [UX6]2-, where X = F, Cl, or Br, we identify RIXS spectral satellites with relative energies and intensities that relate to the extent of uranium-ligand bond covalency. By analyzing the spectra in combination with ligand field density functional theory we find that the sensitivity of the satellites to the nature of metal-ligand bonding is due to the reduction of 5f interelectron repulsion and 4f-5f spin-exchange, caused by metal-ligand orbital mixing and the degree of 5f radial expansion, known as central-field covalency. Thus, this study furthers electronic structure quantification that can be obtained from 3d4f RIXS, demonstrating it as a technique for estimating actinide-ligand covalency.

Development of a novel method for the strengthening and toughening of irradiation-sterilized bone allografts.

Reconstruction of large skeletal defects is a significant and challenging issue. Bone allografts are often used for such reconstructions. However, sterilizing bone allografts by using γ-irradiation, damages collagen and causes the bone to become weak, brittle and less fatigue resistant. In a previous study, we successfully protected the mechanical properties of human cortical bone by conducting a pre-treatment with ribose, a natural and biocompatible agent. This study focuses on examining possible mechanisms by which ribose might protect the bone. We examined the mechanical properties, crosslinking, connectivity and free radical scavenging potentials of the ribose treatment. Human cortical bone beams were treated with varying concentration of ribose (0.06-1.2 M) and γ-irradiation before testing them in 3-point bending. The connectivity and amounts of crosslinking were determined with Hydrothermal-Isometric-Tension testing and High-Performance-Liquid-Chromatography, respectively. The free radical content was measured using Electron Paramagnetic Resonance. Ribose pre-treatment improved the mechanical properties of irradiation sterilized human bone in a pre-treatment concentration-dependent manner. The 1.2 M pre-treatment provided >100% of ultimate strength of normal controls and protected 76% of the work-to-fracture (toughness) lost in the irradiated controls. Similarly, the ribose pre-treatment improved the thermo-mechanical properties of irradiation-sterilized human bone collagen in a concentration-dependent manner. Greater free radical content and pentosidine content were modified in the ribose treated bone. This study shows that the mechanical properties of irradiation-sterilized cortical bone allografts can be protected by incubating the bone in a ribose solution prior to irradiation.

Formation of environmentally persistent free radicals from the heterogeneous reaction of ozone and polycyclic aromatic compounds.

In the 1980s long-lived radical species were identified in cigarette tar. Since then, environmentally persistent free radicals (EPFRs) have been observed in ambient particulate matter, and have been generated in particulate matter generated from internal combustion engines. For the first time, we measure in situ the formation and decay of EPFRs through the heterogeneous reaction of ozone and several polycyclic aromatic compounds (PAC). Solid anthracene (ANT), pyrene (PY), benzo[a]pyrene (BAP), benzo[ghi]perylene (BGHIP), 1,4-naphthoquinone (1,4NQ), and 9,10-anthraquinone (AQ) were reacted with gas-phase ozone in a flow system placed in the active cavity of an electron paramagnetic resonance (EPR) spectrometer, and the formation of radicals was measured on the timescale of tens of minutes at ambient levels of ozone down to 30 ppb. For most substrates the net radical production is initially rapid, slows at intermediate times, and is followed by a slow decay. For oxidized solid BAP, radical signal persists for many days in the absence of ozone. To evaluate the effect of substrate phase, the solid PAHs were also dissolved in squalane, an organic oil inert to ozone, which yielded a much higher maximum radical concentration and faster radical decay when exposed to ozone. With higher mobility, reactants were apparently able to more easily diffuse and react with each other, yielding the higher radical concentrations. The EPR spectra exhibit three radicals types, two of which have been assigned to semiquinone species and one to a PAH-derived, carbon-centered radical. Although our system uses levels of PAC not typically found in the environment it is worth noting that the amounts of radical formed, on the order of 10(18) radicals per g, are comparable to those observed in ambient particulate matter.

CRAPT: an improved version of APT with compensation for variations in JCH.

A modified version of the attached proton test (APT) sequence for (13)C spectral editing, which we call CRisis-APT (CRAPT), is developed and tested on representative organic compounds. CRAPT incorporates (13)C compensation for refocusing inefficiency with synchronized inversion sweeps (CRISIS) pulses in combination with (1)H broadband inversion pulses to give improved compensation for variations in (1)JCH along with improved refocusing efficiency. It is shown that CRAPT gives edited (13)C spectra with only small losses in sensitivity (between 8% and 15% for strychnine, 1, menthol, 2, cholecalciferol, 3, and isotachysterol, 4), compared with basic (13)C spectra obtained on the same compounds. CRAPT also gives significantly better signal/noise than DEPTQ for nonprotonated carbons. Therefore, we conclude that CRAPT is an improvement over APT or DEPTQ or a combination of DEPT135 with a full (13)C spectrum for routine (13)C spectral editing of organic compounds.

Quantifying the influence of 3d-4s mixing on linearly coordinated metal-ions by L2,3-edge XAS and XMCD.

The mixing valence d and s orbitals are predicted to strongly influence the electronic structure of linearly coordinated molecules, including transition metals, lanthanides and actinides. In specific cases, novel magnetic properties, such as single-ion magnetic coercivity or long spin decoherence times, ensue. Inspired by how the local coordination symmetry can engender such novel phenomena, in this study, we focus our attention on dopants (Mn, Fe, Co, Ni, Cu) in lithium nitride to accept innovation from molecular magnetism in a high symmetry P6/mmm solid-state crystal. The linear coordination environment results in strong 3d-4s mixing, proving to be an ideal series to investigate the role of d-s mixing and bonding on electronic structure and magnetism. It is shown that L2,3-edge XAS can be applied to experimentally identify the presence of 3d-4s mixing and the influence this has on the ligand-field splitting. XMCD specifies how spin-orbit coupling is affected. The combined spectroscopies are analysed to determine the effect of 4s mixing with support from ab initio calculations. The results provide new insight of relevance to future applications, including quantum information processing and the sustainable replacement of rare earths in magnets.

The signal/noise of an HMBC spectrum can depend dramatically upon the choice of acquisition and processing parameters.

The effect of various acquisition and processing parameters on the sensitivity of HMBC spectra for typical organic molecules has been systematically investigated. For molecules in the 200-600 molecular weight range, an acquisition time of 0.2 to 0.4 s, a recycle time of no more than 1.0 s, optimization for (n)J(CH) = 8 Hz and 512 time increments (with two- to fourfold linear prediction) are recommended. Some form of sine bell weighting along f2 and either Gaussian or sine bell weighting along f1 is suggested. The use of a 0.1-s acquisition time and/or Gaussian or exponential weighting along f2 can result in dramatic sensitivity loss, particularly for correlation peaks involving protons with complex splitting patterns, and should be avoided.

Return of the lysergamides. Part II: Analytical and behavioural characterization of N6 -allyl-6-norlysergic acid diethylamide (AL-LAD) and (2'S,4'S)-lysergic acid 2,4-dimethylazetidide (LSZ).

Lysergic acid N,N-diethylamide (LSD) is perhaps one of the most intriguing psychoactive substances known and numerous analogs have been explored to varying extents in previous decades. In 2013, N6 -allyl-6-norlysergic acid diethylamide (AL-LAD) and (2'S,4'S)-lysergic acid 2,4-dimethylazetidide (LSZ) appeared on the 'research chemicals'/new psychoactive substances (NPS) market in both powdered and blotter form. This study reports the analytical characterization of powdered AL-LAD and LSZ tartrate samples and their semi-quantitative determination on blotter paper. Included in this study was the use of nuclear magnetic resonance (NMR) spectroscopy, gas chromatography-mass spectrometry (GC-MS), low and high mass accuracy electrospray MS(/MS), high performance liquid chromatography diode array detection and GC solid-state infrared analysis. One feature shared by serotonergic psychedelics, such as LSD, is the ability to mediate behavioural responses via activation of 5-HT2A receptors. Both AL-LAD and LSZ displayed LSD-like responses in male C57BL/6 J mice when employing the head-twitch response (HTR) assay. AL-LAD and LSZ produced nearly identical inverted-U-shaped dose-dependent effects, with the maximal responses occurring at 200 µg/kg. Analysis of the dose responses by nonlinear regression confirmed that LSZ (ED50 = 114.2 nmol/kg) was equipotent to LSD (ED50 = 132.8 nmol/kg) in mice, whereas AL-LAD was slightly less potent (ED50 = 174.9 nmol/kg). The extent to which a comparison in potency can be translated directly to humans requires further investigation. Chemical and pharmacological data obtained from NPS may assist research communities that are interested in various aspects related to substance use and forensic identification. Copyright © 2016 John Wiley & Sons, Ltd.

Visible and Near-Infrared Photothermal Catalyzed Hydrogenation of Gaseous CO2 over Nanostructured Pd@Nb2O5.

The reverse water gas shift (RWGS) reaction driven by Nb2O5 nanorod-supported Pd nanocrystals without external heating using visible and near infrared (NIR) light is demonstrated. By measuring the dependence of the RWGS reaction rates on the intensity and spectral power distribution of filtered light incident onto the nanostructured Pd@Nb2O5 catalyst, it is determined that the RWGS reaction is activated photothermally. That is the RWGS reaction is initiated by heat generated from thermalization of charge carriers in the Pd nanocrystals that are excited by interband and intraband absorption of visible and NIR light. Taking advantage of this photothermal effect, a visible and NIR responsive Pd@Nb2O5 hybrid catalyst that efficiently hydrogenates CO2 to CO at an impressive rate as high as 1.8 mmol gcat-1 h-1 is developed. The mechanism of this photothermal reaction involves H2 dissociation on Pd nanocrystals and subsequent spillover of H to the Nb2O5 nanorods whereupon adsorbed CO2 is hydrogenated to CO. This work represents a significant enhancement in our understanding of the underlying mechanism of photothermally driven CO2 reduction and will help guide the way toward the development of highly efficient catalysts that exploit the full solar spectrum to convert gas-phase CO2 to valuable chemicals and fuels.

Synthesis of feralex a novel aluminum/iron chelating compound.

There is a need for in vivo applicable Fe(3+) and Al(3+) chelation compounds for use as medicines to treat toxic overload conditions of these ions. A novel compound, 2-deoxy-2-(N-carbamoylmethyl-[N'-2'-methyl-3'-hydroxypyrid-4'-one])-D-glucopyranose, designed to chelate Fe(3+) or Al(3+), has been synthesised utilising three naturally occurring products: maltol, glycine and glucosamine. The synthesis is a simple two step process. First, glycine is coupled to maltol by an aminolysis reaction, to yield the intermediate product 1-carboxymethyl -3-hdroxy-2-methylpyrid-4-one, which is joined with glucosamine using a dicyclohexylcarbodiimide promoted peptide coupling method to produce the desired end product, 2-deoxy-2-(N-carbamoylmethyl-[N'-2'-methyl-3'-hydroxypyrid-4'-one])-D-glucopyranose. The latter has been given the trivial name Feralex-G. NMR analysis permitted assignment of frequencies for all carbon and covalently bound hydrogen atoms and was consistent with the proposed structure of the compound. Electron spray Ionisation Mass Spectrometry (ESI-MS) yielded the expected molecular mass of 344. Proton displacement/pH titration analysis yielded three Feralex-G molecules bound to 1 Al(3+) or Fe(3+) over a measurable pH range of 3-10.5. A rapid TLC method to monitor progression of the synthetic procedures is also described.