How Does the Axial Ligand of Cytochrome P450 Biomimetics Influence the Regioselectivity of Aliphatic versus Aromatic Hydroxylation?

How deep is your orbital? Density functional theory studies on the axial ligand effect of aliphatic versus aromatic hydroxylation of ethylbenzene by iron–oxo complexes with a variable axial ligand show that strong (anionic) ligands pull the metal inside the plane of the haeme and destabilise cationic intermediates through orbital interactions (see picture).

     

Determination of senkirkine and senecionine in Tussilago farfara using microwave-assisted extraction and pressurized hot water extraction with liquid chromatography tandem mass spectrometry

Tussilago farfara (Kuan Donghua) is an important Chinese herbal medicine which has been shown to contain many bioactive compounds and widely used to relieve cough and resolve phlegm. However, besides therapeutic bioactive compounds, this herb has been found to contain toxic pyrrolizidine alkaloids (PAs), mainly senkirkine and traces of senecionine. In this report, conditions for microwave-assisted extraction (MAE) and pressurized hot water extraction (PHWE) were optimized for the extraction of the PAs. The results were compared against heating under reflux. It was found that the binary mixture of MeOH:H₂O (1:1) acidified using HCl to pH 2-3 was the optimal solvent for the extraction of the PAs in the plant materials. Liquid chromatography (LC) with ultra-violet (UV) detection and electrospray ionization mass spectrometry (ESI-MS) in the positive mode was used for the determination and quantitation of senkirkine and senecionine in the botanical extract. The proposed extraction methods with LC/MS allow for the rapid detection of the major and the minor alkaloids in T. farfara in the presence of co-eluting peaks. With LC/MS, the quantitative analysis of PAs in the extract was done using internal standard calibration and the precision was found to vary from 0.6% to 5.4% on different days. The limits of detection (LODs) and limits of quantitation (LOQs) for MAE and PHWE were found to vary from 0.26 μg/g to 1.04 μg/g and 1.32 μg/g to 5.29 μg/g, respectively. The method precision of MAE and PHWE were found to vary from 3.7% to 10.4% on different days. The results showed that major and minor alkaloids extracted using MAE and PHWE were comparable to that by heating under reflux. Our data also showed that significant ion suppression was not observed in the analysis of senkirkine and senecionine in the botanical extracts with co-eluting peaks.     

High electrical conductivity for the partially oxidised d8 Ru–Ru bonded chain [Ru(bpy)(CO)2]n (bpy = 2,2′-bipyridine) and its wide range redox control

High, electrochemically controlled electrical conductivity (0.2–0.3 S cm^?1) was measured for the first time for the metal–metal bonded polymeric compound [Ru(bpy)(CO)₂]_n (bpy = 2,2′-bipyridine). The conductivity depended on the degree of partial oxidation of the initially zero-valent Ru to Ru^I in the chains and was found to increase by four orders of magnitude after 5% oxidative doping. Linear conductance vs. doping level dependence was found for low levels and the conductivity of films could repeatedly be switched on and off. The conduction process is ascribed to charge delocalisation on the Ru chains in analogy to that of other similar chains formed by stacking of planar transition metal d⁸ complexes.     

Comparison of in-tube sorptive extraction techniques for non-polar volatile organic compounds by gas chromatography with mass spectrometric detection

A commercial in-tube sorptive extraction device, known as solid-phase dynamic extraction (SPDE), has been evaluated for the extraction of non-polar volatile aromatic analytes from aqueous solutions in both headspace and liquid injection modes. An automated sampler is used with a gas-tight 2.5 ml syringe equipped with a special needle that is coated on the inside with a non-polar extraction phase. After absorption onto the phase, the analytes were thermally desorbed directly into a GC-MS system. The technique was evaluated for the determination of furan, benzene and toluene. The sensitivity for toluene was greatly improved on using SPDE compared to static headspace. A slight increase in sensitivity was observed for benzene but none for determination of furan. Estimated limits of detection ranged from 0.2 to 2 microg/l.     

Carbon nanotube-enhanced separation of DNA fragments by a portable capillary electrophoresis system with contactless conductivity detection

It was demonstrated that separation of DNA fragments by a CE-contactless conductivity detection system (CE-CCD) could be enhanced with multiple-wall carbon nanotubes (MWCNs) as buffer additive. For HaeIII digest of PhiX174 DNA, optimized MWCN concentration was obtained when the MWCN was above its threshold concentration, at which MWCN could form a network in the buffer as pseudostationary phase to provide additional interaction sites. In the case of larger DNA, MWCN near or below its threshold concentration was enough to provide great improvement of the resolution, which was shown by the separation of the 2-Log DNA ladder. Furthermore, the buffer containing MWCN could provide a more stable baseline in the CE-CCD system, owing to less fluctuation of its conductivity. Compared with CE-UV, CE-CCD with MWCN could provide lower LODs as well as better resolution.     

Determination of tobramycin in human serum by capillary electrophoresis with contactless conductivity detection

A study on the determination of the antibiotic tobramycin by CE with capacitively coupled contactless conductivity detection is presented. This method enabled the direct quantification of the non-UV-absorbing species without incurring the disadvantages of the indirect approaches which would be needed for optical detection. The separation of tobramycin from inorganic cations present in serum samples was achieved by optimizing the composition of the acetic acid buffer. Field-amplified sample stacking was employed to enhance the sensitivity of the method and a detection limit of 50 microg/L (S/N = 3) was reached. The RSDs obtained for migration time and peak area using kanamycin B as internal standard were typically 0.12 and 4%, respectively. The newly developed method was validated by measuring the concentration of tobramycin in serum standards containing typical therapeutic concentrations of 2 and 10 mg/L. The recoveries were 96 and 97% for the two concentrations, respectively.     

Microbubble-enhanced hemorrhage control using high intensity focused ultrasound

Our objective was to investigate whether hemorrhage control can be achieved faster when high-intensity focused ultrasound (HIFU) is applied in the presence of ultrasound contrast agents (UCA) as compared to HIFU only application. Incisions (3 cm long and 0.5 cm deep) were produced in the livers of anesthetized rabbits. UCA Optison (0.18 ml/kg) was injected into the mesenteric vein. A HIFU applicator (5.5 MHz, 6800 W/cm² in situ) was scanned at a rate of 1–2 mm/s in one direction over the incision (with multiple passes if needed), until hemostasis was achieved. Hemostasis times were 59 ± 23 s (n = 21) in the presence of Optison and 70 ± 23 s (n = 29) without Optison. The presence of Optison produced on average 37% reduction in hemostasis times normalized to initial bleeding rates (p < 0.05), as well as 60% faster formation of the coagulum seal over the incision (p < 0.05). Gross and histological observations showed similar appearance of HIFU lesions produced in the presence of Optison and HIFU lesions produced without Optison. Our results suggest potential utility of UCA for increasing efficiency of HIFU-induced hemostasis of solid organ injuries.     

Ferromagnetic properties of Fe-substituted ZnO-based magnetic semiconductor

The diluted magnetic semiconductor Zn_1−x⁵⁷Fe_xO (x=0.01, 0.02, 0.03) compounds were prepared by the solid-state reaction method. The crystal structure of _Zn0.97⁵⁷_Fe0.03O${\mathrm{Zn}}_{0.97}{}^{57}{\mathrm{Fe}}_{0.03}\mathrm{O}$ at room temperature is determined to be a hexagonal structure of P6₃mc with lattice constants a₀=3.252 Å and c₀=5.205 Å by Rietveld refinement. The Bragg factors R_B and R_F were determined as 3.23% and 2.81%. From the inverse susceptibility versus T curve, the paramagnetic Curie temperature is found to be 2.7 K and effective moment is found to be 4.01 μ_B, thereby suggesting that the exchange interactions between Fe ions are ferromagnetic. Mössbauer spectra of _Zn0.97⁵⁷_Fe0.03O${\mathrm{Zn}}_{0.97}{}^{57}{\mathrm{Fe}}_{0.03}\mathrm{O}$ have been taken at various temperatures ranging from 4.2 to 295 K. Mössbauer spectrum for _Zn0.97⁵⁷_Fe0.03O${\mathrm{Zn}}_{0.97}{}^{57}{\mathrm{Fe}}_{0.03}\mathrm{O}$ at 4.2 K has shown ferromagnetic phase (sextet), and the spectra were fitted based on a random distribution model of Fe ions.     

The charge structure and interaction mechanism on In-doped sulphur spinel

The charge structure and interaction mechanism on In-doped sulphur spinel FeIn_xCr_2−xS₄ are studied. The temperature dependence of magnetization μ_B, measured from 60 K to room temperature, suggests that FeIn_xCr_2−xS₄ (x=0.1$x=0.1$, 0.3) are ferrimagnetic. The Néel temperature is decreased with increasing non-magnetic In substitution as consequence of reduction of superexchange interaction for increased lattice parameter. FeIn_xCr_2−xS₄ is investigated by Mössbauer spectra from 4.2 K to room temperature. The asymmetric line broadening is observed for the sample FeIn_xCr_2−xS₄ and considered to be dynamic Jahn–Teller relaxation. The charge state of Fe ions is ferrous in character.     

An effective stochastic excitation strategy for finding elusive NMR signals from solids

The versatility of using a stochastic pulse sequence to elucidate peaks with a wide range of shifts, peak widths, and T(1) relaxation times is demonstrated. A stochastic sequence is combined with high speed magic angle spinning (MAS) to obtain the broad and largely shifted peak associated with (31)P in LiNiPO(4). A stochastic sequence is also used to obtain a spectrum of 85% H(3)PO(4), which has a much longer T(1) value. The signal-to-noise was comparable for spectra of 85% H(3)PO(4) obtained with either a stochastic sequence or an optimized Ernst angle experiment. Experimental parameters for the stochastic experiment are set depending only on the ringdown of the probe and not on any inherent qualities of the sample. A stochastic sequence, therefore, combined with MAS provides a useful strategy for finding peaks with unknown T(1) relaxation constants, peak widths, and shifts.