Long-range synthon Aufbau modules (LSAM) in crystal structures: systematic changes in C6H6-nFn (0 <= n <= 6) fluorobenzenes

We discuss the assembly of a three-dimensional molecular crystal in terms of short-range supramolecular synthons that spontaneously organize themselves according to Aufbau principles into long-range geometries characteristic of the molecules themselves. For this purpose we have examined the systematic changes in the known crystal structures of a family of fluorobenzenes, C6H6-nFn, where 0 <= n <= 6. Crystal assembly is initiated by forming long-range synthon Aufbau modules (LSAM) that carry the imprint of the synthons. For example, when 1 <= n <= 5 the short-range synthons use H center dot center dot center dot F interactions to form the LSAMs. In the n = 0 and n = 6 compounds, the synthons are H center dot center dot center dot C and F center dot center dot center dot C interactions, respectively. The LSAMs are usually one-dimensional. In this study we show that these 1D LSAMs assemble into 2D quasi-hexagonal close-packed layers. The 3D crystal structure is obtained from the various kinds of close-packing known for these 2D layers. The final stages of this 1D -> 2D -> 3D assembly seem to be more influenced by the packing of LSAMs than by any other factor. In these final stages, there may not be so much influence exerted by the stronger short-range synthons. We discuss the evolution of these fluorobenzene crystal structures in terms of putative LSAMs and the purely geometric relationships between the n and (6 - n) compounds that can thus be expected. Such particle-hole pairs show structural similarities. Our discussion is quantified by the interpretation of intermolecular distances in terms of atomic sizes and with qualitative predictions of magnetic model systems.

Long-range synthon Aufbau modules (LSAM) in crystal structures: systematic changes in C6H6-nFn (0 <= n <= 6) fluorobenzenes

We discuss the assembly of a three-dimensional molecular crystal in terms of short-range supramolecular synthons that spontaneously organize themselves according to Aufbau principles into long-range geometries characteristic of the molecules themselves. For this purpose we have examined the systematic changes in the known crystal structures of a family of fluorobenzenes, C6H6-nFn, where 0 <= n <= 6. Crystal assembly is initiated by forming long-range synthon Aufbau modules (LSAM) that carry the imprint of the synthons. For example, when 1 <= n <= 5 the short-range synthons use H center dot center dot center dot F interactions to form the LSAMs. In the n = 0 and n = 6 compounds, the synthons are H center dot center dot center dot C and F center dot center dot center dot C interactions, respectively. The LSAMs are usually one-dimensional. In this study we show that these 1D LSAMs assemble into 2D quasi-hexagonal close-packed layers. The 3D crystal structure is obtained from the various kinds of close-packing known for these 2D layers. The final stages of this 1D -> 2D -> 3D assembly seem to be more influenced by the packing of LSAMs than by any other factor. In these final stages, there may not be so much influence exerted by the stronger short-range synthons. We discuss the evolution of these fluorobenzene crystal structures in terms of putative LSAMs and the purely geometric relationships between the n and (6 - n) compounds that can thus be expected. Such particle-hole pairs show structural similarities. Our discussion is quantified by the interpretation of intermolecular distances in terms of atomic sizes and with qualitative predictions of magnetic model systems.

Chemical structural effects on γ-ray spectra of positron annihilation in fluorobenzenes

Spectra of ?-ray Doppler shifts for positron annihilation in benzene and its fluoro-derivatives are simulated using low energy plane wave positron (LEPWP) approximation. The results are compared with available measurements. It is found that the Doppler shifts in these larger aromatic compounds are dominated by the contributions of the valence electrons and that the LEPWP model overestimates the measurements by approximately 30%, in agreement with previous findings in noble gases and small molecules. It is further revealed that the halogen atoms not only switch the sign of the charges on carbon atoms that they bond to, but that they also polarize other C-H bonds in the molecule leading to a redistribution of the molecular electrostatic potentials. As a result, it is likely that the halogen atoms contribute more significantly to the annihilation process. The present study also suggests that, while the Doppler shifts are sensitive to the number of valence electrons in the molecules, they are less sensitive to the chemical structures of isomers that have the same numbers and type of atoms and, hence, the same numbers of electrons. Further investigation of this effect is warranted. © EDP Sciences, Società Italiana di Fisica, Springer-Verlag 2012.

Molecular rearrangement reactions in the gas phase triggered by electron attachment

Bond formation and rearrangement reactions in gas phase electron attachment were studied through dissociative electron attachment (DEA) to pentafluorotoluene (PFT), pentafluoroaniline (PFA) and pentafluorophenol (PFP) in the energy range 0-14 eV. In the case of PFA and PFP, the dominant processes involve formation of [M - HF](-) through the loss of neutral HF. This fragmentation channel is most efficient at low incident electron energy and for PFP it is accompanied by a substantial conformational change of the anionic fragment. At higher energy, HF loss is also observed as well as a number of other fragmentation processes. Thermochemical threshold energies have been computed for all the observed fragments and classical trajectories of the electron attachment process were calculated to elucidate the fragmentation mechanisms. For the dominant reaction channel leading to the loss of HF from PFP, the minimum energy path was calculated using the nudged elastic band method.

Impact of enhanced compliance initiatives on the efficacy of rosuvastatin in reducing low density lipoprotein cholesterol levels in patients with primary hypercholesterolaemia.

The effectiveness of lipid-lowering medication critically depends on the patients' compliance and the efficacy of the prescribed drug. The primary objective of this multicentre study was to compare the efficacy of rosuvastatin with or without access to compliance initiatives, in bringing patients to the Joint European Task Force's (1998) recommended low-density lipoprotein cholesterol (LDL-C) level goal (LDL-C, <3.0 mmol/L) at week 24. Secondary objectives were comparison of the number and percentage of patients achieving European goals (1998, 2003) for LDL-C and other lipid parameters. Patients with primary hypercholesterolaemia and a 10-year coronary heart disease risk of >20% received open label rosuvastatin treatment for 24 weeks with or without access to compliance enhancement tools. The initial daily dosage of 10 mg could be doubled at week 12. Compliance tools included: a) a starter pack for subjects containing a videotape, an educational leaflet, a passport/goal diary and details of the helpline and/or website; b) regular personalised letters to provide message reinforcement; c) a toll-free helpline and a website. The majority of patients (67%) achieved the 1998 European goal for LDL-C at week 24. 31% required an increase in dosage of rosuvastatin to 20 mg at week 12. Compliance enhancement tools did not increase the number of patients achieving either the 1998 or the 2003 European target for plasma lipids. Rosuvastatin was well tolerated during this study. The safety profile was comparable with other drugs of the same class. 63 patients in the 10 mg group and 58 in the 10 mg Plus group discontinued treatment. The main reasons for discontinuation were adverse events (39 patients in the 10 mg group; 35 patients in the 10 mg Plus group) and loss to follow-up (13 patients in the 10 mg group; 9 patients in the 10 mg Plus group). The two most frequently reported adverse events were myalgia (34 patients, 3% respectively) and back pain (23 patients, 2% respectively). The overall rate of temporary or permanent study discontinuation due to adverse events was 9% (n = 101) in patients receiving 10 mg rosuvastatin and 3% (n = 9) in patients titrated up to 20 mg rosuvastatin. Rosuvastatin was effective in lowering LDL-C values in patients with hypercholesterolaemia to the 1998 European target at week 24. However, compliance enhancement tools did not increase the number of patients achieving any European targets for plasma lipids.

β-conglycinin combined with fenofibrate or rosuvastatin have exerted distinct hypocholesterolemic effects in rats

Background: There is increasing interest in non-pharmacological control of cholesterol and triglyceride levels in the plasma and diet-drug association represent an important area of studies. The objective of this study was to observe the hypocholesterolemic effect of soybean β-conglycinin (7S protein) alone and combined with fenofibrate and rosuvastatin, two hypolipidemic drugs. Methods. The protein and drugs were administered orally once a day to rats and the effects were evaluated after 28 days. Wistar rats were divided into six groups (n = 9): hypercholesterolemic diet (HC), HC+7S protein (300 mg.kg-1 day-1) (HC-7S), HC+fenofibrate (30 mg.kg-1 day-1)(HC-FF), HC+rosuvastatin (10 mg.kg-1 day-1)(HC-RO), HC+7S+fenofibrate (HC-7S-FF) and HC+7S+rosuvastatin (HC-7S-RO). Results: Animals in HC-7S, HC-FF and HC-RO exhibited reductions of 22.9, 35.8 and 18.8% in total plasma cholesterol, respectively. In HC-7S-FF, animals did not show significant alteration of the level in HC+FF while the group HC-7S-RO showed a negative effect in comparison with groups taking only protein (HC-7S) or drug (HC-RO). The administration of the protein, fenofibrate and rosuvastatin alone caused increases in the plasma HDL-C of the animals, while the protein-drug combinations led to an increase compared to HC-FF and HC-RO. The plasma concentration of triacylgycerides was significantly reduced in the groups without association, while HC-7S-FF showed no alteration and HC-7S-RO a little reduction. Conclusion: The results of our study indicate that conglycinin has effects comparable to fenofibrate and rosuvastatin on the control of plasma cholesterol, HDL-C and triacylglycerides, when given to hypercholesterolemic rats, and suggests that the association of this protein with rosuvastatin alters the action of drug in the homeostasis of cholesterol. © 2012 Ferreira et al; licensee BioMed Central Ltd.