Doubly-charged ethane ions: Solution to the dilemma of stability predicted by theory and instability observed in experiment

Potential energy curves have been computed for [C2H6]2+ ions and the results used to interpret the conspicuous absence of these ions in 2E mass spectra and in charge-stripping experiments. The energies and structures of geometry-optimized ground-state singlet and excited-state triplet [C2H6]2+ ions have been determined along with energies for different decomposition barriers and dissociation asymptotes. Although singlet and triplet [C2H6]2+ ions can exist as stable entities, they possess low energy barriers to decomposition. Vertical Franck-Condon transitions, involving electron impact ionization of ethane as well as charge-stripping collisions of [C2H6]+ ions, produce [C2H6]2+ ions which promptly dissociate since they are formed with energies in excess of various decomposition barriers. Appearance energies computed for doubly-charged ethane fragment ions are in accordance with experimental values.

Doubly charged ion mass spectra of alkyl-substituted furans and pyrroles

Doubly charged ion mass spectra of alkyl-substituted furans and pyrroles were obtained using a double-focusing magnetic mass spectrometer operated at 3.2 kV accelerating voltage. Molecular ions were the dominant species found in doubly charged spectra of lower molecular weight heterocydic compounds, whereas the spectra of the higher weight homologues were typified by abundant fragment ions from extensive decomposition. Measured doubly charged ionization and appearance energies ranged from 22.8 to 47.9 eV. Ionization energies were correlated with values calculated using self-consistent field–molecular orbital techniques. A multichannel diabatic curve-crossing model was developed to investigate the fundamental organic ion reactions responsible for development of doubly charged ion mass spectra. Probabilities for Landau–Zener type transitions between reactant and product curves were determined and used in the collision model to predict charge-transfer cross-sections, which compared favorably with experimental cross-sections obtained using time-of-flight techniques.

Doubly-charged gas phase cations

Unique features of doubly-charged stable organic ions are examined and the results correlated with experimental observations. Self-consistent field molecular orbital methods are used to compute structures and stabilities of CnH 2 2+ (n=2–9) ions which are prominent in electron impact ionization of hydrocarbon molecules. A simple curve crossing model is employed to rationalize charge transfer reactions of these ions.

Competition between single and double electron transfer in collisions of doubly charged molecular pyrrole ions with neutral pyrrole molecules

Cross-sections have been determined for one- and two-electron transfer channels in the collisions of keV gas-phase doubly charged pyrrole ions with pyrrole molecules. Measured single and double electron transfer total cross-sections approximate 45 Å2 and 15 Å2, respectively. A combination of symmetric resonance charge exchange and multistate curve-crossing models has been invoked to describe these reactions.

Smoking negatively impacts renal cell carcinoma overall and cancer-specific survival

Tobacco use is a leading cause of premature death, yet few studies have investigated the effect of tobacco exposure on the outcome of patients with renal cell carcinoma (RCC). The authors of this report retrospectively studied the impact of smoking on clinicopathologic factors, survival outcomes, and p53 expression status in a large cohort of patients with RCC.

Systemic and hepatic vein galectin-3 are increased in patients with alcoholic liver cirrhosis and negatively correlate with liver function

Recently we demonstrated higher galectin-3 in portal venous serum (PVS) compared to hepatic venous serum (HVS) in a small cohort of patients with normal liver function suggesting hepatic removal of galectin-3. Here, galectin-3 was measured by ELISA in PVS, HVS and systemic venous blood (SVS) of 33 patients with alcoholic liver cirrhosis and a larger cohort of 11 patients with normal liver function. Galectin-3 was cleared by the healthy but not the cirrhotic liver, and subsequently HVS and SVS galectin-3 levels were significantly increased in the patients with liver cirrhosis compared to controls. In healthy liver galectin-3 was produced by cholangiocytes and synthesis by hepatocytes was only observed in cirrhotic liver. Hepatic venous pressure gradient did not correlate with galectin-3 levels excluding hepatic shunting as the principal cause of higher SVS galectin-3. Galectin-3 was elevated in all blood compartments of patients with CHILD-PUGH stage C compared to patients with CHILD-PUGH stage A, and was higher in patients with ascites than patients without this complication. Galectin-3 was negatively associated with antithrombin-3 whose synthesis is reduced with worse liver function. Galectin-3 positively correlated with urea and creatinine, and PVS galectin-3 showed a negative association with creatinine clearance as an accepted measure of kidney function. To summarize in the current study systemic, portal and hepatic levels of galectin-3 were found to be negatively associated with liver function in patients with alcoholic liver cirrhosis and this may in part be related to impaired hepatic removal and/or increased synthesis in cirrhotic liver.

Phosphocreatine interacts with phospholipids, affects membrane properties and exerts membrane-protective effects

A broad spectrum of beneficial effects has been ascribed to creatine (Cr), phosphocreatine (PCr) and their cyclic analogues cyclo-(cCr) and phospho-cyclocreatine (PcCr). Cr is widely used as nutritional supplement in sports and increasingly also as adjuvant treatment for pathologies such as myopathies and a plethora of neurodegenerative diseases. Additionally, Cr and its cyclic analogues have been proposed for anti-cancer treatment. The mechanisms involved in these pleiotropic effects are still controversial and far from being understood. The reversible conversion of Cr and ATP into PCr and ADP by creatine kinase, generating highly diffusible PCr energy reserves, is certainly an important element. However, some protective effects of Cr and analogues cannot be satisfactorily explained solely by effects on the cellular energy state. Here we used mainly liposome model systems to provide evidence for interaction of PCr and PcCr with different zwitterionic phospholipids by applying four independent, complementary biochemical and biophysical assays: (i) chemical binding assay, (ii) surface plasmon resonance spectroscopy (SPR), (iii) solid-state (31)P-NMR, and (iv) differential scanning calorimetry (DSC). SPR revealed low affinity PCr/phospholipid interaction that additionally induced changes in liposome shape as indicated by NMR and SPR. Additionally, DSC revealed evidence for membrane packing effects by PCr, as seen by altered lipid phase transition. Finally, PCr efficiently protected against membrane permeabilization in two different model systems: liposome-permeabilization by the membrane-active peptide melittin, and erythrocyte hemolysis by the oxidative drug doxorubicin, hypoosmotic stress or the mild detergent saponin. These findings suggest a new molecular basis for non-energy related functions of PCr and its cyclic analogue. PCr/phospholipid interaction and alteration of membrane structure may not only protect cellular membranes against various insults, but could have more general implications for many physiological membrane-related functions that are relevant for health and disease.

Investigating The Fate Of Positively Charged Nanoparticles In A Soil Environment

The recent increase in the amount of nanoparticles incorporated into commercial products is accompanied by a rising concern of the fate of these nanoparticles. Once released into the environment, it is inevitable that the nanoparticles will come into contact with the soil, introducing them to various routes of environmental contamination. One route that was explored in this research was the interaction between nanoparticles and clay minerals. In order to better define the interactions between clay minerals and positively charged nanoparticles, in situ atomic force microscopy (AFM) was utilized. In situ AFM experiments allowed interactions between clay minerals and positively charged nanoparticles to be observed in real time. The preliminary results demonstrated that in situ AFM was a reliable technique for studying the interactions between clay minerals and positively charged nanoparticles and showed that the nanoparticles affected the swelling (height) of the clay quasi-crystals upon exposure. The preliminary AFM data were complemented by batch study experiments which measured the absorbance of the nanoparticle filtrate after introduction to clay minerals in an effort to better determine the mobility of the positively charged nanoparticles in an environment with significant clay contribution. The results of the batch study indicated that the interactions between clay minerals and positively charged nanoparticles were size dependent and that the interactions of the different size nanoparticles with the clay may be occurring to different degrees. The degree to which the different size nanoparticles were interacting with the clay was further probed using FTIR (Fourier transform infrared) spectroscopy experiments. The results of these experiments showed that interactions between clay minerals and positively charged nanoparticles were size dependent as indicated by a change in the FTIR spectra of the nanoparticles upon introduction to clay.