Fast Dissolution Dynamic Nuclear Polarization NMR of 13C-Enriched 89Y-DOTA Complex: Experimental and Theoretical Considerations

The yttrium complex of 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetra(1′-¹³C-acetic acid) [¹³C]DOTA was synthesized. Fast dissolution dynamic nuclear polarization (DNP) nuclear magnetic resonance (NMR) studies revealed that the ⁸⁹Y, ¹³C, and ¹⁵N nuclei present in the complex could be co-polarized at the same optimum microwave irradiation frequency. The liquid-state spin–lattice relaxation time T ₁ of these nuclei were found to be reasonably long to preserve some or most of the DNP-enhanced polarization after dissolution. The hyperpolarized ¹³C and ⁸⁹Y NMR signals were optimized in different glassing mixtures. The overall results are discussed in light of the thermal mixing model of DNP.     

Spontaneous Phosphorus‐Halogen Bond Cleavage in N‐Heterocyclic Halogenophosphanes Revisited: The Case of P–Br and P–I Bonds

P‐bromo‐ and P‐Iodo‐substituted N‐heterocyclic phosphanes (NHP) were synthesized by halogen exchange starting from the P‐chloro compound and characterized by spectroscopic data and X‐ray diffraction studies. Whereas the Br‐NHP still forms a molecular crystal, the solid‐state structure of the I‐derivative consists of ion‐pairs which assemble via secondary P···I interactions to form one‐dimensional coordination polymers. Computational studies indicate that the bond dissociation is due to a combination of intramolecular stabilisation (aromatisation of the phosphenium cation formed) and intermolecular Lewis‐acid/base interactions. Reaction of the I‐NHP with I₂ proceeded under complete P–I bond cleavage to give an ionic phosphenium triiodide whose single‐crystal X‐ray diffraction study revealed a unique supramolecular structure.     

Measuring polymer surface ordering differences in air and water by sum frequency generation vibrational spectroscopy

Molecular structures of poly(n-butyl methacrylate) (PBMA) at the PBMA/air and PBMA/water interfaces have been studied by sum frequency generation (SFG) vibrational spectroscopy. PBMA surfaces in both air and water are dominated by the methyl groups of the ester side chains. The average orientation and orientation distribution of these methyl groups at the PBMA/air and PBMA/water interfaces are different, indicating that surface restructuring occurs when the PBMA sample contacts water. Analysis shows that the orientation distribution of side chain methyl groups on the PBMA surface is narrower in water than that in air, indicating that the PBMA surface can be more ordered in water. To our knowledge, this is the first time that quantitative comparisons between molecular surface structures of polymers in air and in water have been made. Two assumptions on the orientation distribution function, including a Gaussian distribution and a formula based on the maximum entropy approach, are used in the analysis. It has been found that the orientation angle distribution function deduced by the Gaussian distribution and the maximum entropy distribution are quite similar, showing that the Gaussian distribution is a good approximation for the angle distribution. The effect of experimental error on the deduced orientational distribution is also discussed.     

Rapid identification of allergen-encoding cDNA clones by phage display and high-density arrays

We describe a high-throughput, quantitative technology for fast identification of all different clones present in selectively enriched phage surface-displayed cDNA libraries. The strategy is based on a combination of phage display and high-density arrays. To demonstrate the utility of the method cDNAs of Aspergillus fumigatus cloned into phagemid pJuFo were expressed on the tip of filamentous M13 phage and affinity-selected on solid phase-immobilized serum IgE from allergic patients. Enriched phagemid libraries were amplified in bacteria, plated and arrayed into 384-well microtitre plates by robotic colony picking. cDNA inserts were amplified by high-throughput PCR and gridded onto high-density filter membranes. Filters were iteratively probed with randomly-sequenced inserts until all clones were identified. Eighty-one different sequences encoding IgE-binding proteins likely to cover a large part of the allergen repertoire of the mould were found. This approach represents a widely applicable method for rapid high-throughput identification of all individual cDNAs present in selectively enriched libraries.     

Interaction of Pesticides with a β-Cyclodextrin Derivative Studied by Reversed-phase Thin-layer Chromatography and Principal Component Analysis

The interaction of 18 pesticides with a water-soluble -cyclodextrin polymer (BCDP) was studied by reversed-phase thin-layer chromatography and principal component analysis (PCA) was employed for the elucidation of the relationship between the relative strength of interaction and the calculated surface parameters of the guest molecules. Except for penconazole the lipophilicity of the pesticides decrease in the presence of BCDP. PCA indicated that apolar surface parameters are highly positively correlated with the strength of interaction. The data indicate that the agrochemical characteristics (adsorption, leakage, decomposition, etc) of complexed pesticide molecules can be different from those of uncomplexed onesresulting in modified efficacy.     

Isotope selective analysis of CO(2) with tunable diode laser (TDL) spectroscopy in the NIR

The performance of a home-built tunable diode laser (TDL) spectrometer, aimed at multi-line detection of carbon dioxide, has been evaluated and optimized. In the regime of the (30(0)1)(III) <-- (000) band of (12)CO(2) around 1.6 microm, the dominating isotope species (12)CO(2), (13)CO(2), and (12)C(18)O(16)O were detected simultaneously without interference by water vapor. Detection limits in the range of few ppmv were obtained for each species utilizing wavelength modulation (WM) spectroscopy with balanced detection in a long-path absorption cell set-up. High sensitivity in conjunction with high precision -- typically +/-1 (per thousand) and +/-6 (per thousand) for 3% and 0.7% of CO(2), respectively -- renders this experimental approach a promising analytical concept for isotope-ratio determination of carbon dioxide in soil and breath gas. For a moderate (12)CO(2) line, the pressure dependence of the line profile was characterized in detail, to account for pressure effects on sensitive measurements.     

Preparation of ultrasmall, uncapped PbS quantum dots via electroporation of vesicles

Electric-field-induced transient pore formation (electroporation) in synthetic unilamellar dioleoylphosphatidylcholine vesicles of 178-nm diameter is utilized for the preparation of subnanometer-size PbS quantum dots. With Pb2+ ions originally entrapped in the vesicles and S2- ions placed in the bulk, their reaction is initiated by the opening of pores and occurs in the bulk. The ensuing self-aggregation of PbS is slowed to the hour and day time scales by its adsorption at the exterior surface of the vesicles. The growth of the particles in the molecular size regime is found to exhibit novel, time-dependent, oscillating red and blue shifts of the characteristic UV absorption band. On the basis of similarities between the oscillating trend of the experimentally observed transition energy and that of the calculated highest occupied molecular orbital-lowest unoccupied molecular orbital gap of (PbS)n clusters with n = 1-9, the wavelengths of the sequential spectral peaks can be assigned to the PbS monomer (237.5 nm), dimer (282 nm), tetramer (232 nm), hexamer (281 nm), octamer (234.5 nm), and nonamer (278-280 nm). Growth beyond the octamer is associated with the customary monotonic red shift of the absorption band. Under the experimental conditions used, a stable system is reached with unchanging spectral features after 20 days. This solution is estimated to contain 1.82 x 10(-5) M (PbS)9 particles, each with a greatest dimension of <9 A.