Localization of Fatty Acyl and Double Bond Positions in Phosphatidylcholines Using a Dual Stage CID Fragmentation Coupled with Ion Mobility Mass Spectrometry

A high content molecular fragmentation for the analysis of phosphatidylcholines (PC) was achieved utilizing a two-stage [trap (first generation fragmentation) and transfer (second generation fragmentation)] collision-induced dissociation (CID) in combination with travelling-wave ion mobility spectrometry (TWIMS). The novel aspects of this work reside in the fact that a TWIMS arrangement was used to obtain a high level structural information including location of fatty acyl substituents and double bonds for PCs in plasma, and the presence of alkali metal adduct ions such as [M?+?Li]⁺ was not required to obtain double bond positions. Elemental compositions for fragment ions were confirmed by accurate mass measurements. A very specific first generation fragment ion m/z 577 (M-phosphoryl choline) from the PC [16:0/18:1 (9Z)] was produced, which by further CID generated acylium ions containing either the fatty acyl 16:0 (C₁₅H₃₁CO⁺, m/z 239) or 18:1 (9Z) (C₁₇H₃₃CO⁺, m/z 265) substituent. Subsequent water loss from these acylium ions was key in producing hydrocarbon fragment ions mainly from the α-proximal position of the carbonyl group such as the hydrocarbon ion m/z 67 (+H₂C-HC?=?CH-CH?=?CH₂). Formation of these ions was of important significance for determining double bonds in the fatty acyl chains. In addition to this, and with the aid of ¹³C labeled lyso-phosphatidylcholine (LPC) 18:1 (9Z) in the ω-position (methyl) TAP fragmentation produced the ion at m/z 57. And was proven to be derived from the α-proximal (carboxylate) or distant ω-position (methyl) in the LPC.     

Practical synthesis of (2'R)-2'-deoxy-2'-C-methyluridine by highly diastereoselective homogeneous hydrogenation

Diastereoselective hydrogenation of 2'-deoxy-2'-exo-methyleneuridine was carried out under homogeneous conditions using a low loading of a chiral Rh catalyst. This, coupled with improvements in the synthesis of the substrate, allowed the smooth pilot plant preparation of the title compound on >10 kg scale.     

A FLUORESCENCE IMAGING DEVICE FOR ENDOSCOPIC DETECTION OF EARLY STAGE CANCER – INSTRUMENTAL and EXPERIMENTAL STUDIES

Abstract Visible detection of early stage cancer labelled with the fluorescing porphyrin mixture of dihematoporphyrin-ether and dihematoporphyrin-ester (DHE) is often limited by a high and inhomogeneously distributed level of autofluorescence. A new imaging method for reducing autofluo-rescence is described. The method uses alternating fluorescence excitation with laser light in the violet and blue spectral ranges. Subtraction of the corresponding fluorescence images results in contrast enhancement due to an effective reduction in the autofluorescence contribution. A prototype version of a highly sensitive fluorescence imaging device including a modified krypton ion laser, an image-intensified solid-state TV-camera, a digital image-processing system, and video recording and monitoring has been developed.
Experiments performed with this fluorescence imaging system on a tumorous dog bladder showed that a dose of 0.2 mg DHE kg⁻¹ body wt, which is far below the dose administered for photodynamic therapy (2-5 mg kg⁻'body wt), is sufficient to give a high-contrast fluorescence image. The corresponding excitation power density was about 1 W m⁻². Photobleaching of DHE was observed during fluorescence detection at excitation power densities exceeding 1 kW m⁻². At these high excitation levels DHE fades out nearly completely within 0.25 min.     

On the zeros of the Scorer functions

Asymptotic approximations are developed for zeros of the solutions Gi(z) and Hi(z) of the inhomogeneous Airy differential equation . The solutions are also called Scorer functions. Tables are given with numerical values of the zeros.     

Matrix Effects on Selective Chemical Sensing by Sol-Gel Entrapped Complexing Agents

Changes in the selectivity of molecular recognition systems on sol-gel entrapment are reported. Thermodynamic effects are exemplified by studies of the metal-ion complexing agent Eriochrome Cyanine R (ECR). In aqueous solution this binds strongly and selectively to Al3+, whereas in a TMOS-based sol-gel matrix it is selective for Cu3+. Thermodynamic effects, due to restricted translational freedom of water molecules or different solvent structure and isolation of ligands, can explain these observations. Effects of entrapment on molecular recognition by a large conformationally flexible molecule have been studied using a tris-terminated PAMAM dendrimer. The dendrimer conformation and its complexation with Cu2+ changes on entrapment, and binding of aromatic carboxylic acids such as ibuprofen can be detected by changes in visible absorption and surface plasmon resonance using spun films of the sol-gel composite. These effects show that in addition to providing a porous entrapment matrix of good optical quality, sol-gels may be used to alter the binding characteristics of the entrapped receptors.