Spectroscopic characterization of the oxo-transfer reaction from a bis(mu-oxo)dicopper(III) complex to triphenylphosphine

The oxygen-atom transfer reaction from the bis(mu-oxo)dicopper(III) complex [Cu(III)(2)(mu-O)(2)(L)(2)](2+), where L =N,N,N',N' -tetraethylethylenediamine, to PPh(3) has been studied by UV-vis, EPR, (1)H NMR and Cu K-edge X-ray absorption spectroscopy in parallel at low temperatures (193 K) and above. Under aerobic conditions (excess dioxygen), 1 reacted with PPh(3), giving O=Ph(3) and a diamagnetic species that has been assigned to an oxo-bridged dicopper(II) complex on the basis of EPR and Cu K-edge X-ray absorption spectroscopic data. Isotope-labeling experiments ((18)O(2)) established that the oxygen atom incorporated into the triphenylphosphine oxide came from both complex 1 and exogenous dioxygen. Detailed kinetic studies revealed that the process is a third-order reaction; the rate law is first order in both complex 1 and triphenylphosphine, as well as in dioxygen. At temperatures above 233 K, reaction of 1 with PPh(3) was accompanied by ligand degradation, leading to oxidative N-dealkylation of one of the ethyl groups. By contrast, when the reaction was performed in the absence of excess dioxygen, negligible substrate (PPh(3)) oxidation was observed. Instead, highly symmetrical copper complexes with a characteristic isotropic EPR signal at g= 2.11 were formed. These results are discussed in terms of parallel reaction channels that are activated under various conditions of temperature and dioxygen.     

Identification and comparative determination of senkyunolide A in traditional Chinese medicinal plants Ligusticum chuanxiong and Angelica sinensis by HPLC coupled with DAD and ESI-MS

Using the HPLC/DAD/ESI/MS method, the qualitative and quantitative analysis of senkyunolide A (SA) in the rhizomes of Ligusticum chuanxiong (Rhizoma chuanxiong; CX) and roots of Angelica sinensis (DG) was established. As a result, it was found that SA is a characteristic standard compound for the quality evaluation and chemical differentiation between CX and DG. Methanol was chosen in the preparation of standard solutions and extraction of samples based on the stability data. The identity of SA in CX and DG was unambiguously determined based on the quasimolecular ions in ESI-MS. A comprehensive validation of the method, including sensitivity, linearity, reproducibility and recovery, was conducted using the optimized chromatographic conditions. The linear calibration curve was acquired with R2>0.999 and limit of detection (S/N=3) was estimated to be 12.5 mug/g. The reproducibility was evaluated by repeated sample injection and replicated analysis of samples with the relative standard deviation (RSD) value found within 0.68%. The recovery rates of SA varied within the range of 96.91-101.50% with RSD less than 2.38%. In the present work, the contents of SA were quantified within 3.94-9.14 mg/g and 0.108-0.588 mg/g for 12 batches each of CX and DG. The results demonstrated that SA is a useful standard compound for the quality evaluation and chemical differentiation between CX and DG. The analytical procedure is precise and reproducible and thus suitable for the analysis of a large number of samples.     

Silylated derivatives of arabinonucleosides

Procedure have been developed which allow for the selective derivatization of arabinonucleosides at the 5′? or 2′? and 5′? or 3′? and 5′? positions.     

Precise measurement of the 23P0−23P2 fine structure interval in helium

A measurement of the 2³P₀?2³P₂ fine structure interval in the helium has beeen made using the optical microwave atomic beam magnetic resonance technique. The result is 31.908 040 (20) GHz (0.6ppm), which establishes an internal consistency in measurements of the helium fine structure and verifies the theory to order α⁴Ry. When the theory is used together wit our experimental result we obtain a value for the fine structure constant α by α^-1=137.03613(11) (0.8 ppm).     

Configurational analysis of rotational states in the SD shell

It is shown that the shell-model states belonging to a given rotational band in ²³Na and ²⁴Mg have very similar subshell occupancies, different bands being characterised by different occupancies. On the one hand this establishes a connection, somewhat different from that provided by the SU (3) scheme, between the spherical shell model and the idea of an intrinsic state, and on the other hand helps discriminate between possible candidates for membership of a band and imposes limits on the lengths of the bands.     

Quadrupole moments of the first excited states of 204,206Pb

The static quadrupole moments of the first excited states of ^204,206Pb are measured to be +0.23 ± 0.09 and +0.05 ± 0.09 eb, respectively. These results, together with measured B(E2; 0⁺ → 2⁺) values, are interpreted in terms of the systematics of nuclear deformation in the A ≈ 200 mass region.     

The synthesis of phosphite analogues of ribonucleotides

The synthesis of compounds having a phosphite bridge between nucleoside units, their characteristics toward phosphodiesterases, their conversion to normal nucleotides and their use in oligonucleotide synthesis is described.     

Two-wire waveguide and interferometer for cold atoms

A versatile miniature de Broglie waveguide is formed by two parallel current-carrying wires in the presence of a uniform bias field. We derive a variety of analytical expressions to describe the guide and present a quantum theory to show that it offers a remarkable range of possibilities for atom manipulation on the submicron scale. These include controlled and coherent splitting of the wave function as well as cooling, trapping, and guiding. In particular, we discuss a novel microscopic atom interferometer with the potential to be exceedingly sensitive.