Synthesis and properties of new ditertiary stibines based upon o-, m- or p-xylyl and m- or p-phenylene backbones and their complexes with tungsten, iron and nickel carbonyls

High yield syntheses for 1,2-, 1,3-, and 1,4-xylyl distibines (1,2-C6H4(CH2SbMe2)2, 1,3-C6H4(CH2SbMe2)2, 1,4-C6H4(CH2SbMe2)2, respectively) from Me2SbCl (conveniently made in situ from Me2PhSb and HClgas) and the appropriate di-Grignard are reported. The 1,3- and 1,4-phenylene distibines, 1,3-C6H4(SbMe2)2 and 1,4-C6H4(SbMe2)2, were made similarly. The new ligands have been characterised by mass spectrometry, 1H and 13C[1H] NMR spectroscopy, and by the preparation of methiodide derivatives. The crystal structures of 1,4-C6H4(CH2SbMe2)2 and [1,3-C6H4(CH2SbMe3)2]I2 have been determined. The synthesis of 1,2-C6H4(CH2SbPh2)2 has been achieved similarly in modest yield and the distibine converted into the tetra-iodo-derivative 1,2-C6H4(CH2SbPh2I2)2. The coordination modes available to these ligands have been probed by the synthesis and characterisation of complexes with nickel, iron and tungsten carbonyls. The crystal structure of [[Fe(CO)4]2[micro-1,3-C6H4(CH2SbMe2)2]] has been determined. The spectroscopic properties of these carbonyl derivatives have been compared with those of complexes of other antimony ligands, and in some cases with diphosphine and diarsine complexes, to probe the electronic properties of the new ligands.     

Synthesis of the tetrahydroisoquinoline alkaloid (+/-)-renieramycin G and A (+/-)-lemonomycinone analogue from a common intermediate

The total synthesis of tetrahydroisoquinoline alkaloids (+/-)-renieramycin G (4) and a lemonomycinone analogue (7) is described. A general strategy to synthesize both the mono- and bistetrahydroisoquinoline alkaloids from a common advanced intermediate, 17, is presented.     

Structural characteristics and residual stresses in oxide films produced on Ti by pulsed unipolar plasma electrolytic oxidation

Oxide films, 7–10 µm thick, were produced on commercially pure titanium by plasma electrolytic oxidation in a sodium orthophosphate electrolyte using a pulsed unipolar current with frequency (f) and duty cycle (δ) varying within f = 0.1–10 kHz and δ = 0.8–0.2, respectively. The coatings comprised a mixture of an amorphous phase with nanocrystalline anatase and rutile phases, where the relative rutile content range was 17–25 wt%. Incorporation of phosphorus from the electrolyte into the coating in the form of PO₂ ^–, PO₃ ^2– and PO₄ ^3–, as demonstrated by EDX and FT-IR analyses, contributed to the formation of the amorphous phase. Residual stresses associated with the crystalline coating phase constituents were evaluated using the X-ray diffraction sin² ψ method. It was found that, depending on the treatment parameters, internal direct and shear stresses in anatase ranged from–205 (±17) to–431 (±27) MPa and from–98 (±6) to–145 (±10) MPa, respectively, whereas the rutile structure is comparatively stress-free.     

High-resolution in vivo imaging of blood vessels without labeling

We demonstrate that both oxyhemoglobin and deoxyhemoglobin have sequential two-color, two-photon absorption properties that can serve as endogenous contrasts in microvasculature imaging. Using a sensitive modulation transfer technique, we are able to image hemoglobin in red blood cells with micrometer resolution, both in vitro and in vivo. We show that excellent contrast from hemoglobin without any labeling can be obtained in tissue.     

Surface activity and self-aggregation ability of three cationic quaternized aminocalix[4]arenes

The self-aggregation ability of three amphiphilic cationic calix[4]arenes possessing four quaternary amino groups (aminoCAs) was investigated using a variety of methods. All of the studied compounds possess high aggregation ability. Their critical aggregation concentration (CAC) values in water are in the 0.0009–0.04 % (w/v) concentration range. Several size populations of aggregates were detected by DLS for all three CAs, and restructuring of aggregates was observed to be dependent on concentration. Particles formed above CAC were attributed to formation of vesicular structures (vesicles). The coexistence of other type of aggregates (presumably micelles) with vesicles was observed in the aqueous solution of CAs 2 and 3 from concentrations of 0.5 and 0.8 % (w/v), respectively. The filtration procedure was found to be a significant factor since the obtained data from filtered and unfiltered samples was different. The particle sizes obtained by TEM measurements were somewhat correlated with the DLS data for unfiltered CAs solutions. An analysis of the aggregate composition was undertaken by a size-exclusion method using semi-permeable cellophane membranes with different MWCO. A negative deviation from linearity of permeability flux profile starting from 0.8 % (w/v) concentration of donor phase indicated that the fraction of large aggregates at this point is significant enough that the molecules could not easily permeate through the membranes.     

Self-collimation and beam splitting in low-index photonic crystals

We study self-collimation and beam splitting in low-refractive-index photonic crystals created within chalcogenide glass. We propose a beam splitter structure that allows direct experimental verification of photonic-crystal effects at optical wavelengths in a straightforward and definitive manner. The beam splitter provides angular separation of 90° using a highly compact spatial footprint, thus delivering direct application in highly integrated photonic devices.     

The3He(γ,2p)n reaction for Eγ=80-170MeV

The cross section for the³He(γ, 2p) reaction has been measured in a complete kinematics experiment in the energy rangeE _γ=80–170 MeV, forθ _P1=θ _P2=90°. This configuration was selected in order to investigate the role of proton-proton final state interactions in the three-body breakup process. The measured proton spectra are seen to be consistent with a prediction using the Watson-Migdal formalism. The magnitude of the observed cross section clearly indicates an enhancement over phase space, presumably due to the strong proton-proton interaction in the final state. The experimental results agree, within their limited statistical accuracy, with a theoretical calculation which includes this effect.     

Is there a universal scale of time?

The assumption that the same universal scale of time applies for different physical laws depends uponthe hypothesis that there is a unique universal scale of time in the universe. Intrinsic to that hypothesis is the assumption that if extraneous factors that affect physical clocks and processes that run on different physical principles could be removed, all clocks are synchronizable with one another. The consequences of that hypothesis not being true are considered. It was found thatclock asynchrony implies that: (1) a mass variation theory is probable; (2) there is a need for multiple clocks; and (3) t in the equations of physics is referring to clocks rather than time such that the properties of time are reduced to its direction (as characterized by thermodynamics and cosmology).     

Proton spectra from the 6,7Li(γ,p) 5,6He reactions at Eγ = 60 MeV

The ${}^{\mathrm{6,7}}\text{Li}\text{(γ,}\text{p}\text{)}$ reactions have been investigated for E_γ = 60 MeV. Excitation of residual (1p)^?1 and (1s)^?1 hole states is evident from the proton spectra measured at ?_p = 45°. The data are compared with a theoretical calculation which includes short-range correlations.