A cytotoxic substance from Sangre de Grado

Taspine has been isolated as a cytotoxic substance from Sangre de Grado, sap of Croton palanostigma (Euphorbiaceae), by bioassay guided fractionation. The cytotoxicity (IC50) of taspine was found to be 0.39 microgram/ml against KB cells and 0.17 microgram/ml against V-79 cells.     

Measurement of the decay and time-resolved spectra of the emission from σ-excitons in KBr in the nanosecond range,produced by heavy-ion irradiation

While energetic heavy ions are currently in increasing use in solid state physics, radiation chemistry and biology, there is still little experimental information regarding the primary physicochemical processes. These high LET (linear energy transfer) ion particles injected into condensed matter produce short life-intermediates such as excited states, ions, and radicals, at high density along the track. The density effect of these intermediates may cause damage-formation and chemical reaction to yield different results compared with low LET radiation (γ, X-ray) or photo-irradiation. Electronically excited states, among the above intermediates, are thought to be especially important precursors. Measurements of the decay and time-resolved spectra of the emission are expected to give useful information regarding the radiation action of heavy ions. The measurements were done using a KBr single crystal at 4.2 K. We reported previously [1] that heavy ion irradiated KBr results in an extraordinarily large ratio of σ-emission to π-emission 2 intensity (～ 5 times larger than in the X- or electron-irradiation). This large ratio is, as was ascertained previously, not due to apparent processes such as temperature increase of a track but to intrinsic processes which will be discussed here.     

Determination of beryllium in copper-beryllium alloys by flow-injection spectrophotometry

Summary A method is described for the flow-injection spectrophotometric determination of beryllium in Cu-Be-alloys using xylenol orange as reagent. Cu, Co and Fe are masked by means of thiosulphate and EDTA. Absorbance is measured at the maximum of 493 nm. With a flow rate of 4 ml/min 60 samples can be analyzed per hour with a relative standard deviation of about 1%.

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Bestimmung von Beryllium in Cu-Be-Legierungen durch Flow-Injection-Spektralphotometrie

Zusammenfassung Als Reagens zur spektralphotometrischen Bestimmung von Berryllium in Cu-Be-Legierungen dient Xylenolorange. Cu, Co und Fe werden mit Hilfe von Thiosulfat und EDTA maskiert. Die Messung erfolgt im Absorptionsmaximum des Komplexes von 493 nm. Bei einer Durchflußgeschwindigkeit von 4 ml/min können 60 Proben je Stunde mit einer relativen Standardabweichung von etwa 1% analysiert werden.

     

Revised model core potentials for second-row transition metal atoms from Y to Cd

We have produced new relativistic model core potentials (spdsMCPs) for the second-row transition-metal atoms from Y to Cd treating explicitly 4s and 4p electrons in addition to 4d and 5s electrons in the same manner as for the first-row transition-metal atoms given in [Y. Osanai, M.S. Mon, T. Noro, H. Mori, H. Nakashima, M. Klobukowski, E. Miyoshi, Chem. Phys. Lett. 452 (2008) 210]. Using suitable correlating functions together with the split valence MCP functions, we demonstrate that the present MCP basis sets show reasonable performance in predicting the electronic structures of atoms and molecules, bringing about accurate excitation energies for atoms and reasonable spectroscopic constants for AgH.     

Synthesis of a stable iminium salt and propellane derivatives

The treatment of morphinan 1 with NaH and MsCl provided very stable iminium salt 7 possessing propellane skeleton. One of the synthesized iminium salts 7, isobutyl derivative 7b, was crystallized and its structure was determined by X-ray crystallography. The natural bond orbital analysis suggested that the stability of the iminium should result from the stereoelectronic effect (hyperconjugation) attributed to their own structures.     

Construction of Pt complex within Zr-based MOF and its application for hydrogen production under visible-light irradiation

The present article deals with Pt complex construction within Zr-based MOF having bipyridine units in the framework (Zr-MOF-bpy-PtCl₂) and its photocatalytic activity for hydrogen production under visible-light irradiation (λ > 420 nm). Zr-MOF-bpy-PtCl₂ is prepared by the construction of a Zr-based MOF using 2,2′-bipyridine-5,5′-dicarboxylic acid (Zr-MOF-bpy), and subsequent complexation reaction with K₂PtCl₄. XRD and N₂ adsorption–desorption measurements have revealed that both Zr-MOF-bpy and Zr-MOF-bpy-PtCl₂ have a UiO-type structure. From the results of UV–Vis and XAFS measurements, the incorporated Pt species has been proven to be in square planar geometry involving two N atoms and two Cl atoms as a result of the Pt coordination with bipyridine units in the framework. Zr-MOF-bpy-PtCl₂ has been employed for a hydrogen production reaction from water containing a sacrificial electron donor under visible-light irradiation (λ > 420 nm). Zr-MOF-bpy-PtCl₂ realizes steady hydrogen production, and the amount of evolved hydrogen reaches 8.3 μmol after the 9 h reaction period, while Zr-MOF-bpy exhibits no photocatalytic activity under the same conditions. It has also been found that the activity of Zr-MOF-bpy-PtCl₂ is superior to that of the corresponding homogeneous complex analogue (bpy)PtCl₂.     

Selective cleavage of allyl and propargyl ethers to alcohols catalyzed by Ti(O-i-Pr)4/MXn/Mg

[reaction: see text] Allyl and propargyl ethers were effectively deallylated or depropargylated to the parent alcohols via a C-O bond cleavage catalyzed by a low-valent titanium reagent (LVT), Ti(O-i-Pr)4/TMSCl/Mg or Ti(O-i-Pr)4/MgBr2/Mg, under mild reaction conditions. Differentiation between the allyl and propargyl ethers was achieved by the reaction in the presence of AcOEt as an additive. The reagent also catalyzed intra- and intermolecular cyclotrimerization reactions of alkynes to substituted benzenes.     

Parallelized integral-direct CIS(D) calculations with multilayer fragment molecular orbital scheme

We have developed a parallelized integral-direct code of the perturbative doubles correction for configuration interaction with singles, proposed as CIS(D) by Head-Gordon et al. (Chem Phys Lett 219:21, 1994). The CIS(D) method provides the energy corrections both of the relaxation and differential correlation for the respective CIS excited states. The implementation of CIS(D) is based on our original algorithm for the second-order Møller–Plesset perturbation (MP2) calculations (Mochizuki et al. in Theor Chem Acc 112:442, 2004). There is no need to communicate bulky intermediate data among worker processes of the parallelized execution. This CIS(D) code is then incorporated into a developer version of ABINIT-MP program, in order to improve the overestimation in excitation energies calculated by the CIS method in conjunction with the multilayer fragment molecular orbital scheme (MLFMO-CIS) (Mochizuki et al. in Chem Phys Lett 406:283, 2005). The MLFMO-CIS(D) method is first used in evaluating the lowest n\(\pi^{*}\) excitation energy of the hydrated formaldehyde. The photoactive yellow protein (PYP) is the second target of MLFMO-CIS(D) calculation. Through these applications, it is shown that the CIS(D) correction improves the CIS results favorably.     

Benzyl radical addition reaction through the homolytic cleavage of a benzylic C-H bond

Direct generation of a benzyl radical by C-H bond activation of toluenes and the addition reaction of the resulting radical to an electron deficient olefin were developed. The reaction of dimethyl fumarate with toluene in the presence of Et(3)B as a radical initiator at reflux afforded 2-benzylsuccinic acid dimethyl ester in good yield.