Chemical profiles of birch and alder bark by ambient mass spectrometry

Desorption atmospheric pressure photoionization (DAPPI) is an ambient mass spectrometry (MS) technique that allows the analysis of both polar and nonpolar compounds directly from the surfaces of various sample types. Here, DAPPI was used to study the chemical profiles in different parts of birch and alder tree barks. Four distinct fractions of Betula pendula (silver birch) bark were collected from three different developmental stages of the stem, after which the chemical profiles of the different tissue types were measured. Of special interest were triterpenoids, a class of important defensive substances, which are found in the bark of the silver birch. Additionally, the chemical profiles of lenticels and the surrounding surfaces in the phellem of B. pendula (silver birch), Alnus glutinosa (black alder), and Alnus incana (gray alder) were screened with DAPPI. Another ambient MS technique, laser ablation atmospheric pressure photoionization (LAAPPI), was further used for the mass spectrometry imaging of lenticels on the B. pendula phellem. All the studied birch bark fractions showed individual chemical profiles in DAPPI. The mass spectra from the young apical stem and the transition zone resembled each other more than the mature stem. Instead, the phellem was found to contain a high amount of triterpenoids in all the developmental stages of the stem. The most intense peaks in the DAPPI mass spectra of the birch bark fractions were those of betulin and lupeol. Betulinic and betulonic acid peaks were intense as well, and these compounds were detected especially in the lenticels of the tree samples.

Graphical abstract

     

A Requirement for Bid for Induction of Apoptosis by Photodynamic Therapy with a Lysosome- but Not a Mitochondrion-targeted Photosensitizer

Photodynamic therapy (PDT) with lysosome-targeted photosensitizers induces the intrinsic pathway of apoptosis via the cleavage and activation of the BH3-only protein Bid by proteolytic enzymes released from photodisrupted lysosomes. To investigate the role of Bid in apoptosis induction and the role of damaged lysosomes on cell killing by lysosome-targeted PDT, we compared the responses of wild type and Bid-knock-out murine embryonic fibroblasts toward a mitochondrion/endoplasmic reticulum-binding photosensitizer, Pc 4, and a lysosome-targeted sensitizer, Pc 181. Whereas apoptosis and overall cell killing were induced equally well by Pc 4-PDT in both cell lines, Bid^−/− cells were relatively resistant to induction of apoptosis and to overall killing following PDT with Pc 181, particularly at low PDT doses. Thus, Bid is critical for the induction of apoptosis caused by PDT with the lysosome-specific sensitizers, but dispensable for PDT targeted to other membranes.     

Proton affinities of ketones, vicinal diketones and α-keto esters: a computational study

The proton affinities of seven different ketones, vicinal diketones, and α-keto esters (acetophenone, 2,2,2-trifluoroacetophenone, 2,3-butanedione, 1-phenyl-1,2-propanedione, methyl pyruvate, ethyl benzoylformate, and ketopantolactone) have been evaluated theoretically using the conventional ab initio HF and several post-HF methods (MP2, MP4, CCSD), density functional methods with the B3LYP hybrid functional, as well as some ab initio model chemistries [CBS-4M, G2(MP2), and G3(MP2)//B3LYP]. The chemical compounds studied are frequently used substrates in the asymmetric hydrogenation over chirally modified platinum catalysts where the protonation properties of the chiral modifier and the substrates are of great interest. In most cases, the proton affinities (PAs) evaluated with the CCSD/6-311+G(d,p)//B3LYP/TZVP and G2(MP2) methods are in good agreement with the existing experimental ones. However, the previously reported PA of 2,3-butanedione seems to be too high by 10-15 kJ mol⁻¹. The B3LYP/TZVP//B3LYP/TZVP and MP2/6-311+G(d,p)//B3LYP/TZVP model chemistries predict proton affinities that are systematically higher and lower than the experimental PAs, respectively. If proton affinities are evaluated as the average of the PAs calculated with these two theoretical methods a very good agreement with the experimental results is obtained. The mean absolute deviation (MAD) from experiment of this combination method for the PAs of 13 test molecules is 4.0 kJ mol⁻¹. For 9 molecules composed only of first-row atoms the MAD is 2.5 kJ mol⁻¹. The B3LYP/TZVP//B3LYP/TZVP and MP2/6-311+G(d,p)//B3LYP/TZVP methods provide significant savings in computational time and disk space compared to the CCSD/6-311+G(d,p)//B3LYP/TZVP and G2(MP2) models. Therefore, it is suggested that if no experimental or highly accurate theoretical data is available (due to computational cost), the proton affinities of similar compounds as investigated in this paper, can be evaluated with the combination method. For the studied molecules, this method gives the following PAs (in kJ mol⁻¹): 788 (2,3-butanedione, exptl 802); 798 (2,2,2-trifluoroacetophenone, exptl 799); 811 (ketopantolactone); 813 (methyl pyruvate); 825 (1-phenyl-1,2-propanedione); 862 (acetophenone, exptl 861); 865 (ethyl benzoylformate).     

Positron detrapping from defects: A thermodynamic approach

The rate of positron detrapping in thermal equilibrium from lattice defects has been calculated by relating it to the specific trapping rate. The results for vacancies, dislocations and surfaces each show a different temperature dependence for the escape rate. For vacancies a measure of the importance of the detrapping can be obtained from the ratio of the vacancy formation energy to the positron binding energy in the defect. The positronium desorption rate from a surface is also calculated and agreement with experimental results is found.     

In-beam γ-ray spectroscopy of <Superscript>190</Superscript>Po: First observation of a low-lying prolate band in Po isotopes

Gamma rays from excited states of ¹⁹⁰Po have been observed using the Jurosphere Ge-detector array coupled to the RITU gas-filled separator. They were associated with a collective band which from spin 4 onwards resembles the prolate rotational bands known in the isotones ¹⁸⁸Pb and ¹⁸⁶Hg. This indicates that in ¹⁹⁰Po the prolate configuration becomes yrast above I = 2. The experimental results are interpreted in a two-band mixing calculation and are in agreement with α-decay data and potential energy surface calculations. Received: 10 January 2003 / Accepted: 19 February 2003 / Published online: 7 May 2003     

Essential norms and weak compactness of integration operators

The aim of this paper is to present a general method to construct projective resolutions of globally defined Mackey functors over a field of characteristic zero and apply it to obtain explicit resolutions for inflation functors. Our method is a special case of Bouc’s method in (Proc. Symp. Pure Math. 63 (1998), 31–84) and uses global Mackey functors to construct the projective resolutions.     

Current-density imaging using ultra-low-field MRI with adiabatic pulses

Magnetic resonance imaging (MRI) allows measurement of electric current density in an object. The measurement is based on observing how the magnetic field of the current density affects the associated spins. However, as high-field MRI is sensitive to static magnetic field variations of only the field component along the main field direction, object rotations are typically needed to image three-dimensional current densities. Ultra-low-field (ULF) MRI, on the other hand, with B₀ on the order of 10–100 μT, allows novel MRI sequences. We present a rotation-free method for imaging static magnetic fields and current densities using ULF MRI. The method utilizes prepolarization pulses with adiabatic switch-off ramps. The technique is designed to reveal complete field and current-density information without the need to rotate the object. The method may find applications, e.g., in conductivity imaging. We present simulation results showing the feasibility of the sequence.     

The Gaussian free field and Hadamard’s variational formula

We relate the Gaussian free field on a planar domain to the variational formula of Hadamard which explains the change of the Green function under a perturbation of the domain. This is accomplished by means of a natural integral operator—called the Hadamard operator—associated with a given flow of growing domains.