Extrapolation and series acceleration procedures: Hard spheres and discs as illustrations

Three new procedures - in the context of estimation of virial coefficients and summation of the partial virial series for hard discs and hard spheres - are proposed. They are based on the parametrised Euler transformation, a novel resummation, identity and the ?-convergence methods respectively. A comparison with other estimates (molecular dynamics, graph theory and empirical methods) reveals satisfactory agreement.     

Isolation,Characterisation and Oxidation of Isomeric Ferrelactone Complexes.

Irradiation of 1,2-epoxy-l-vinylcyclopentane (1) in the presence of Fe(CO)₅ leads to the formation of isomeric $\text{syn}$-and $\text{anti}$- ferrelactones (2) and (3). The structures of these complexes were determined by X-ray crystallographic methods and on oxidation gave different ratios of β- and δ-lactones.     

PITANSEMA-MAS, a solid-state NMR method to measure heteronuclear dipolar couplings under MAS

A 2D NMR method is presented for the measurement of the dipole-dipole interaction between a proton and a low-frequency nuclear spin species in the solid state under the magic angle spinning. It employs the time averaged nutation concept to dramatically reduce the required radio frequency (rf) power on the low γ nuclear channel and spin exchange at the magic angle is used to suppress (1)H-(1)H dipolar interactions and chemical shifts. The flexibility in choosing the spinning speed, rf power and the scaling factor of the pulse sequence are of considerable importance for the structural studies of biological solids. The performance of the pulse sequence has been numerically and experimentally demonstrated on several solids.     

Development of electrochemical labelling procedures using MEK extracted99mTc

Electrolytic labelling procedures have been reported for various^99mTc radiopharmaceuticals which differ widely in the choice of the electrodes, working pH, applied voltage and the quantity of current passed. The authors have studied the electrolytic labelling of^99mTc EHDP, gluconate and glucoheptonate with MEK extracted^99mTc using tin electrodes under different experimental conditions. The results have, shown that these compounds can be efficiently labelled with^99mTc in a single step procedure avoiding multiple pH adjustments. Labelling of human serum albumin microspheres suitable for lung imaging with^99mTc by the electrolytic method is also reported.     

Effects of antidepressants on the conformation of phospholipid headgroups studied by solid-state NMR

The effect of tricyclic antidepressants (TCA) on phospholipid bilayer structure and dynamics was studied to provide insight into the mechanism of TCA-induced intracellular accumulation of lipids (known as lipidosis). Specifically we asked if the lipid-TCA interaction was TCA or lipid specific and if such physical interactions could contribute to lipidosis. These interactions were probed in multilamellar vesicles and mechanically oriented bilayers of mixed phosphatidylcholine-phosphatidylglycerol (PC-PG) phospholipids using (31)P and (14)N solid-state NMR techniques. Changes in bilayer architecture in the presence of TCAs were observed to be dependent on the TCA's effective charge and steric constraints. The results further show that desipramine and imipramine evoke distinguishable changes on the membrane surface, particularly on the headgroup order, conformation and dynamics of phospholipids. Desipramine increases the disorder of the choline site at the phosphatidylcholine headgroup while leaving the conformation and dynamics of the phosphate region largely unchanged. Incorporation of imipramine changes both lipid headgroup conformation and dynamics. Our results suggest that a correlation between TCA-induced changes in bilayer architecture and the ability of these compounds to induce lipidosis is, however, not straightforward as imipramine was shown to induce more dramatic changes in bilayer conformation and dynamics than desipramine. The use of (14)N as a probe was instrumental in arriving at the presented conclusions.     

Amyloid fiber formation and membrane disruption are separate processes localized in two distinct regions of IAPP, the type-2-diabetes-related peptide

Aggregation of Islet Amyloid Polypeptide (IAPP) has been implicated in the development of type II diabetes. Because IAPP is a highly amyloidogenic peptide, it has been suggested that the formation of IAPP amyloid fibers causes disruption of the cellular membrane and is responsible for the death of beta-cells during type II diabetes. Previous studies have shown that the N-terminal 1-19 region, rather than the amyloidogenic 20-29 region, is primarily responsible for the interaction of the IAPP peptide with membranes. Liposome leakage experiments presented in this study confirm that the pathological membrane disrupting activity of the full-length hIAPP is also shared by hIAPP 1-19. The hIAPP 1-19 fragment at a low concentration of peptide induces membrane disruption to a near identical extent as the full-length peptide. At higher peptide concentrations, the hIAPP 1-19 fragment induces a greater extent of membrane disruption than the full-length peptide. Similar to the full-length peptide, hIAPP 1-19 exhibits a random coil conformation in solution and adopts an alpha-helical conformation upon binding to lipid membranes. However, unlike the full-length peptide, the hIAPP 1-19 fragment did not form amyloid fibers when incubated with POPG vesicles. These results indicate that membrane disruption can occur independently from amyloid formation in IAPP, and the sequences responsible for amyloid formation and membrane disruption are located in different regions of the peptide.     

Two-dimensional homonuclear chemical shift correlation established by the cross-relaxation driven spin diffusion in solids

A new type of spin diffusion, cross-relaxation driven spin diffusion (CRDSD), is investigated using (15)N NMR on a N-acetyl-L-valyl-L-leucine (NAVL) single crystal under stationary condition. A two-dimensional (2D) pulse sequence that correlates the chemical shifts of (15)N nuclei, with a radio-frequency spin lock on the (15)N channel during the mixing time, is used to observe CRDSD. Experimental results obtained using CRDSD, rf-driven spin diffusion, and proton driven spin diffusion approaches on the NAVL single crystal are compared. Our experimental results suggest that the (15)N spin diffusion rate can be enhanced by about 1000 times using CRDSD than by the normal proton driven spin diffusion. Interestingly, the required spin-locking rf field strength for CRDSD is much lower than that used for the rf-driven spin diffusion experiments. The cross-peak patterns observed in 2D (15)N-(15)N correlation spectra using CRDSD and RFDSD are very different as they arise from different spin-spin interactions. A detailed theory describing CRDSD and RFDSD processes is also presented using a thermodynamic model. The speedy spin diffusion process rendered by the CRDSD approach will be useful to assign resonances from a uniformly (15)N or (13)C labeled proteins and peptides, particularly in aligned samples.     

Synthesis of high refractive‐index melt‐stable aromatic polyphosphonates

The synthesis of aromatic polyphosphonates based on the step polymerization of various bisphenols and dichlorophenyl phosphine oxide was investigated. The effect of catalyst, type, concentration, and polymerization time were systematically varied to obtain high molecular weight polymers. Very high molecular weight tough, ductile materials with a high degree of optical clarity were synthesized. In contrast with the aromatic polycarbonates, the refractive index was increased from 1.58 to 1.60 (for the bisphenol A‐based system) and 1.64 for a biphenol‐based system. The latter was still an amorphous soluble polymer as a result of the non‐coplanar nature of the phenyl phosphine oxide bond, unlike the analogous polycarbonate. Hydrolytically stable melt‐processable cumyl phenol end‐capped polyphosphonates were successfully achieved for the first time. Rheological studies show that these end‐capped systems are melt‐stable at 200 °C, whereas the systems of initially higher molecular weight but without any well‐defined end capping clearly degraded quickly probably as a result of an acid‐catalyzed hydrolysis process. Extensive high char yields were produced upon pyrolysis in either nitrogen or air, suggesting good fire resistance. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2904–2910, 2001