Chemical shift reagents in the study of polycyclic alcohols IX—1H NMR spectra of myrtenol and some other primary alcohols

Structure proof of (—)-myrtenol, 3-cyclopentenyl-1-methanol and 5-norbornene-2-endo-methanol has been obtained from their proton magnetic resonance spectra in carbon tetrachloride containing different added amounts of tris(dipivaloylmethanato)europium. For each alcohol, a 1:1 complex structure with Eu(dpm)₃ could be computed, in which the calculated pseudocontact shift effects on all skeleton protons of the ring system were consistent with the observed shift effect values. A considerable contact contribution of opposite sign to that of the pseudocontact part of the effect could be estimated for the methylene protons of the CH₂OH group.     

Collection and behaviour of radon progenies on thin Mylar foils

Thin Mylar foils are often used to protect detectors from contamination. However, these foils can be electrostatically charged, possibly leading to their contamination with airborne radon progenies. In the present work, the collection and behaviour of radon progenies on Mylar foils was investigated in detail using alpha spectrometry. The radon progenies collection rate of a small Mylar foil (3 cm²) is equivalent to an air sampler with a flow rate of approximately 0.1 m³/h. It was demonstrated that such contamination may jeopardise the validity of the entire analysis if not interpreted correctly.     

Improved surface stability and biotin binding properties of streptavidin coating on polystyrene

The ultimate nature of streptavidin to bind biotin tightly is widely utilized in many solid-phase based applications to provide a universal binding surface for biotinylated molecules. However, the preparation of the streptavidin coatings by passive adsorption may heavily alter the binding properties of native streptavidin and may not result in the best possible capture surface for demanding solid-phase assays. By introducing sulphydryl groups through primary amines in the protein, we have activated and conjugated native streptavidin into larger protein polymers resulting in high local binding density when coated on polystyrene. This thiolated streptavidin formed through chemical modification has improved adsorption properties and biotin binding capability, compared to the native streptavidin. When this thiolated streptavidin is coated on polystyrene, a dense surface is formed, which provides up to 3-fold increase in the biotin binding efficiency and improves the surface stability by minimizing the desorption of the adsorbed protein from the surface during incubation. Furthermore, this high-capacity surface is resistant to harsh chemical treatments, such as denaturing conditions or mild reducing conditions. The improved adsorption properties of the thiolated streptavidin allow the coating process to be performed with shorter incubation times (15 min), still providing enhanced solid-phase properties, compared to a reference streptavidin surface.     

Fluorine-free organoxenon chemistry: HXeCCH,HXeCC, and HXeCCXeH

Three novel Xe-containing organic compounds, HXeCCH, HXeCC (open-shell species), and HXeCCXeH, are identified using infrared absorption spectroscopy. They are prepared in a low-temperature Xe matrix using UV photolysis of acetylene and subsequent annealing at 40-45 K. The experimental observations are supported by extensive ab initio calculations. This work demonstrates a new way to activate the H-Ctbd1;C- group without use of XeF(2), which can extend the range of organoxenon compounds.     

Search for B+/--->[K(-/+)pi(+/-)](D)K+/- and upper limit on the b-->u amplitude in B+/--->DK+/-

We search for B+/--->[K(-/+)pi(+/-)](D)K+/- decays, where [K(-/+)pi(+/-)](D) indicates that the K-/+pi(+/-) pair originates from the decay of a D0 or D (0). Results are based on 120x10(6) Upsilon(4S)-->BB decays collected with the BABAR detector at SLAC. We set an upper limit on the ratio R(Kpi) identical with[Gamma(B+-->[K(-)pi(+)](D)K+)+Gamma(B--->[K(+)pi(-)](D)K-)][Gamma(B+-->[K(+)pi(-)](D) / K+)+Gamma(B--->[K(-)pi(+)](D)K-)]<0.026 (90% C.L.). This constrains the amplitude ratio r(B) identical with|A(B--->D 0K-)/A(B--->D0K-)|<0.22 (90% C.L.), consistent with expectations. The small value of r(B) favored by our analysis suggests that the determination of the Cabibbo-Kobayashi-Maskawa phase gamma from B-->DK will be difficult.     

Measurements of CP-violating asymmetries in B0-->K(0)(s)pi(0) decays

We present a measurement of the time-dependent CP-violating (CPV) asymmetries in B0-->K(0)(S)pi(0) decays based on 124x10(6) Upsilon(4S)-->BB decays collected with the BABAR detector at the PEP-II asymmetric-energy B factory at SLAC. In a sample containing 122+/-16 signal decays, we obtain the magnitudes of the direct CPV asymmetry CK(0)(S)(pi(0))=0.40(+0.27)(-0.28)+/-0.09 and of the CPV asymmetry in the interference between mixing and decay SK(0)(S)(pi(0))=0.48(+0.38)(-0.47)+/-0.06 where the first error is statistical and the second systematic.     

Atmospheric aerosol studies in southern Norway using size-fractonating smapling devices and nuclear analytical techniques

Atmospheric aerosol samples were collected during spring sampling campaigns in 1988 and 1989 at Birkenes and Nordmoen in southern Norway. The aerosol collectors used included stacked filter units (SFUs), a low volume sampler (referred to as ILVS), which consists of a filter preceded by three impaction stages, and an 11-stage Berner low-pressure impactor (LPI). All samples were analyzed for up to about 40 elements by INAA and PIXE. The resuls obtained from parallel samplings were intercompared in terms of ratios ILVS/SFU and LPI/SFU, whereby these ratios were calculated separately for the coarse and fine size fractions. For the ILVS/SFU parallel samplings, excellent agreement was observed between the results for the fine fraction, with the overall mean average ratio (based on 21 samples and 22 elements) being 0.99±0.10. For the coarse fraction, the overall mean ILVS/SFU ratio (based on 21 elements) was 0.75±0.13. This low result is explained by different upper-particle-size cut-offs of the two samplers. For the parallel samplings with LPI and SFU, the agreement was poorer, but still reasonable. The atmospheric concentrations observed at the two sites in the two campaigns and also the LPI size distributions for the various elements are discussed briefly.     

Chemical compounds formed from diacetylene and rare-gas atoms: HKrC4H and HXeC4H

New organic rare-gas compounds, HRgC4H (Rg = Kr or Xe), are identified in matrix-isolation experiments supported by ab initio calculations. These compounds are the largest molecules among the known rare-gas hydrides. They are prepared in low-temperature rare-gas matrixes via UV photolysis of diacetylene and subsequent thermal mobilization of H atoms at approximately 30 and 45 K for Kr and Xe, respectively. The strongest IR absorption bands of the HRgC4H molecules are the H-Rg stretches with the most intense components at 1290 cm(-1) for HKrC4H and at 1532 cm(-1) for HXeC4H, and a number of weaker absorptions (C-H stretching, C-C-C bending, and C-C-H bending modes) are also found in agreement with the theoretical predictions. As probably the most important result, the IR absorption spectra indicate some further stabilization of the HRgC4H molecules as compared with the corresponding HRgC2H species identified recently (Khriachtchev et al. J. Am. Chem. Soc. 2003, 125, 4696 and Khriachtchev et al. J. Am. Chem. Soc. 2003, 125, 6876). The computational energetic results support this trend. HXeC4H is predicted to be 2.5 eV lower in energy than H + Xe + C4H, which is approximately 1 eV larger than the corresponding value for HXeC2H. We expect that the larger molecules HRgC6H and HRgC8H are even more stable and the HRgC2nH species are good candidates for bulk organic rare-gas material.     

Synthesis of Lanthanide(III) Chelates by Using ‘Click’ Chemistry

The copper(I)‐catalyzed dipolar [2+3] cycloaddition reaction of an azide and a terminal alkyne is exploited in the preparation of various europium(III), terbium(III), and dysprosium(III) chelates (Schemes 1–3). By changing the nature of the alkyne and the azide, a wide range of chelates and biomolecule‐labeling reactants were obtained. The photophysical properties (Table) of the synthesized chelates are also discussed.     

Luminescence of Europium(III) Chelates with 4-(Arylethynyl)pyridines as Ligands

Some Spectral properties and luminescence intensities of Eu^III chelates with 4-(arylethynyl)pyridine-2,6-dicarboxylic acids 1 – 15 and 2,2′,2″,2′″-{[4-(arylethynyl)pyrridine-2,6-diyl]bis(methylenenitrilo)} tetrakis(acetic acids) 16 – 26 were measured both in H₂O and EtOH solutions for the purpose of developing suitable labels to be used in time-resolved luminescence-based bioaffinity assays (Tables 1 and 2). The substitution at the Ar group has a significant effect upon the observed luminescence intensities, excitation wavelengths, and decay constants of the complexes, Moreover, the changes in the environment cause great variation in those properties of certain Eu^III chelates.