Critical exponents for NMR and ESR linewidths in a two-dimensional antiferromagnet

The exponent p in ΔH ∝ (T/T_N?1)^-p is derived both for NMR and ESR linewidths ΔH in a two-dimensional antiferromagnet. The approach is based on Kawasaki's dynamical equations. Comparison is made with experiments on K₂NiF₄ and K₂MnF₄.     

Photoionisation cross-section calculations for satellite processes: Relaxed Hartree—Fock theory with application to helium n = 2 lines

The calculation of photoionisation cross-sections for atomic diagram and satellite transitions in a relaxed-orbital Hartree—Fock framework within the dipole approximation is considered, with specific numerical application to the helium system. The length, velocity and acceleration forms of the dipole operator are investigated. A reformulation of the dipole-operator expression is required for conjugate shake-up processes to ensure that the ratio of the various dipole forms is independent of photon energy at the Hartree—Fock level. The most suitable treatment produces cross-sections of accuracy comparable to experimental precision for the diagram transition at photon energies down to threshold, and for satellite transitions down to 15 eV above threshold. On the basis of the present findings, electron correlation contributions other than relaxation effects may not be as important as previously thought in contributing to satellite intensities in singly ionised systems, except in the threshold region.     

Determination of pharmaceutical compounds in skin by imaging matrix-assisted laser desorption/ionisation mass spectrometry

Matrix-assisted laser desorption/ionisation (MALDI) quadrupole time-of-flight mass spectrometry (Q-TOFMS) has been used to detect and image the distribution of a xenobiotic substance in skin. Porcine epidermal tissue was treated with 'Nizoral', a medicated shampoo containing ketoconazole (+/-)-1-acetyl-4-[p-[[(2R,4S)-2-(2,4-dichlorophenyl)-2-(imidazol-1-ylmethyl)-1,3-dioxolan-4-yl]methoxy]phenyl]piperazine) as active ingredient. Following incubation for 1 h at 37 degrees C all excess formulation was washed from the surface. A cross-section of the drug-treated tissue was then blotted onto a cellulose membrane, precoated in matrix (alpha-cyano-4-hydroxycinnamic acid (CHCA)), by airspray deposition. In separate experiments the tissue surface was treated with Nizoral within a triangular former, and subsequently blotted onto a matrix-coated membrane. Sample membranes were then mounted into the recess of specialised MALDI targets with adhesive tape. All samples were analysed by MALDI-TOFMS using an Applied Biosystem 'Q-star Pulsar i' hybrid Q-TOF mass spectrometer fitted with an orthagonal MALDI ion source and imaging software. Detection of the protonated molecule was readily achievable by this technique. Treatment of the tissue within a template gave rise to images depicting the expected distribution of the drug, demonstrating that this technique is capable of producing spatially useful data. Ion images demonstrating the permeation of the applied compound into the skin were achieved by imaging a cross-sectional imprint of treated tissue. A calibration graph for the determination of ketoconazole was prepared using the sodium adduct of the matrix ion as an internal standard. This enabled construction of a quantitative profile of drug in skin. Conventional haematoxylin and eosin staining and microscopy methods were employed to obtain a histological image of the porcine epidermal tissue. Superimposing the mass spectrometric and histological images appeared to indicate drug permeation into the dermal tissue layer.     

Heritability of Stroop and flanker performance in 12-year old children

Background  

There is great interest in appropriate phenotypes that serve as indicator of genetically transmitted frontal (dys)function, such as ADHD. Here we investigate the ability to deal with response conflict, and we ask to what extent performance variation on response interference tasks is caused by genetic variation. We tested a large sample of 12-year old monozygotic and dizygotic twins on two well-known and closely related response interference tasks; the color Stroop task and the Eriksen flanker task. Using structural equation modelling we assessed the heritability of several performance indices derived from those tasks.     

Characterization of Ar'Sn(micro-Br)Sn(Ar')CH2C6H4-4-Pri (Ar' = C6H3-2,6-Dipp2; Dipp = C6H3-2,6-Pri2): a stable structural analogue for a heavier group 14 element monobridged alkene isomer HM(micro-H)MH2 (M = Sn or Pb)

The title compound is the first stable structural analogue for the monobridged isomer of a heavier group 14 alkene analogue.     

High average power,all-solid-state external resonator Raman laser

As much as 3 W of average power at 1064 nm from a diode-pumped Nd:YAG laser, Q switched at 4 kHz, was used to pump an external-resonator, crystalline Ba(NO3)2 Raman laser generating a maximum of 1.3-W output at the first Stokes wavelength of 1197 nm. The slope efficiency was 63% with respect to the fundamental power incident on the Ba(NO3)2 crystal. A reduction in the beam quality of the Stokes output from M2 approximately 1.4 at lower Stokes powers to M2 approximately 3.4 at higher powers is attributed to thermal loading of the Raman-active crystal.     

Synthesis of monodentate ferrocenylphosphines and their application to the palladium-catalyzed Suzuki reaction of aryl chlorides

Racemic and enantiopure ((p)()S)-1-bromo-2-methylferrocene 6 were synthesized in 4 steps from 2-(4,4-dimethyloxazolinyl)ferrocene and (S)-2-(4-methylethyloxazolinyl)ferrocene, respectively (46 and 81% overall yield). Bromolithium exchange and addition of ClPR(2) gave the corresponding racemic or enantiopure 2-methylferrocenyl phosphine ligands 2-MeFcPR(2) 11 (R = Ph), 12 (R = Cy), and 13 (R = (t)Bu) in 28-93% yield. Use of PCl(3) gave the C(3)-symmetric phosphine (2-MeFc)(3)P 5 from ((p)()S)-6(72% yield) but racemic 6 did not lead to the formation of triferrocenyl phosphines. Combination of 5 and Pd(2)(dba)(3) gave an active catalyst for the Suzuki reaction of aryl chlorides, for example, 4-chlorotoluene and phenylboronic acid reacted at only 60 degrees C in dioxane (86% yield). Other examples are reported together with the use of 12 in this same protocol. From the X-ray crystal structure of 5 the cone angle was determined as 211 degrees. With this, and the electronic character of 11, 12, and other phosphines (derived from nu(CO) of trans-[(R(3)P)(2)Rh(CO)Cl]), an analysis is made of the steric and electronic influences on ligand activity in the Suzuki reaction.