Gauging the Strength of the Molecular Halogen Bond via Experimental Electron Density and Spectroscopy.

Strong and weak halogen bonds (XBs) in discrete aggregates involving the same acceptor are addressed by experiments in solution and in the solid state. Unsubstituted and perfluorinated iodobenzenes act as halogen donors of tunable strength; in all cases, quinuclidine represents the acceptor. NMR titrations reliably identify the strong intermolecular interactions in solution, with experimental binding energies of approx. 7 kJ/mol. Interaction of the σ hole at the halogen donor iodine leads to a redshift in the symmetric C-I stretching vibration; this shift reflects the interaction energy in the halogen-bonded adducts and may be assessed by Raman spectroscopy in condensed phase even for weak XBs. An experimental picture of the electronic density for the XBs is achieved by high-resolution X-ray diffraction on suitable crystals. Quantum theory of atoms in molecules (QTAIM) analysis affords the electron densities and energy densities in the bond critical points of the halogen bonds and confirms stronger interaction for the shorter contacts. For the first time, the experimental electron density shows a significant effect on the atomic volumes and Bader charges of the quinuclidine N atoms, the halogen-bond acceptor: strong and weak XBs are reflected in the nature of their acceptor atom. Our experimental findings at the acceptor atom match the discussed effects of halogen bonding and thus the proposed concepts in XB activated organocatalysis.

Photo-Responsive Control of Adsorption and Structure Formation at the Air-Water Interface with Arylazopyrazoles.

Smart interfaces that are responsive to external triggers such as light are of great interest for the development of responsive or adaptive materials and interfaces. Using alkyl-arylazopyrazole butyl sulfonate surfactants (alkyl-AAP) that can undergo E/Z photoisomerization when irradiated with green (E) and UV (Z) lights, we demonstrate through a combination of experiments and computer simulations that there can be surprisingly large changes in surface tension and in the molecular structure and order at air-water interfaces. Surface tensiometry, vibrational sum-frequency generation (SFG) spectroscopy, and neutron reflectometry (NR) are applied to the study of custom-synthesized AAP surfactants with octyl- and H-terminal groups at air-water interfaces as a function of their bulk concentration and E/Z configuration. Upon photoswitching, a drastic influence of the alkyl chain on both the surface activity and the responsiveness of interfacial surfactants is revealed from changes in the surface tension, γ, where the largest changes in γ are observed for octyl-AAP (Δγ ∼ 23 mN/m) in contrast to H-AAP with Δγ < 10 mN/m. Results from vibrational SFG spectroscopy and NR show that the interfacial composition and the molecular order of the surfactants drastically change with E/Z photoisomerization and surface coverage. Indeed, from analysis of the S-O (head group) and C-H vibrational bands (hydrophobic tail), a qualitative analysis of orientational and structural changes of interfacial AAP surfactants is provided. The experiments are complemented by resolution of thermodynamic parameters such as equilibrium constants from ultra-coarse-grained simulations, which also capture details like island formation and interaction parameters of interfacial molecules. Here, the interparticle interaction ("stickiness") and the interaction with the surface are adjusted, closely reflecting experimental conditions.

NMR relaxometry of oil paint binders.

Mobile nuclear magnetic resonance (NMR) is a flexible technique for nondestructive characterization of water in plants, the physical properties of polymers, moisture in porous walls, or the binder in paintings by relaxation measurements. NMR relaxation data report material properties and therefore can also help to characterize the state of tangible cultural heritage. In this work, we discuss the relaxation behavior in two series of naturally aged paint mock-up samples. First, paints with different pigment concentrations were prepared and investigated in terms of the longitudinal and transverse relaxation-time distributions. We document the evolution of both relaxation-time distributions during the initial drying stage and demonstrate the heightened importance of transverse over longitudinal relaxation measurements. Second, we observe nonlinear dependences of the relaxation times on the pigment concentration in a typical oil binder. Third, in a study of naturally aged paint samples prepared in the years between 1914 and 1951 and subsequently aged under controlled conditions, we explore the possibility of determining the age of paintings using partial least square regression (PLS) by fitting T1 -T2 data with the sample age. Our results suggest some correlation, albeit with significant scatter. Estimating the age of a painting stored under unknown conditions from NMR relaxation data is therefore not feasible, as the cumulative effects of light irradiation, humidity, and biological degradation further obfuscate the chemical and physical impact of aging on the relaxation times in addition to the impact of pigment concentration.

Physical exercise in overweight to obese individuals induces metabolic- and neurotrophic-related structural brain plasticity.

Previous cross-sectional studies on body-weight-related alterations in brain structure revealed profound changes in the gray matter (GM) and white matter (WM) that resemble findings obtained from individuals with advancing age. This suggests that obesity may lead to structural brain changes that are comparable with brain aging. Here, we asked whether weight-loss-dependent improved metabolic and neurotrophic functioning parallels the reversal of obesity-related alterations in brain structure. To this end we applied magnetic resonance imaging (MRI) together with voxel-based morphometry and diffusion-tensor imaging in overweight to obese individuals who participated in a fitness course with intensive physical training twice a week over a period of 3 months. After the fitness course, participants presented, with inter-individual heterogeneity, a reduced body mass index (BMI), reduced serum leptin concentrations, elevated high-density lipoprotein-cholesterol (HDL-C), and alterations of serum brain-derived neurotrophic factor (BDNF) concentrations suggesting changes of metabolic and neurotrophic function. Exercise-dependent changes in BMI and serum concentration of BDNF, leptin, and HDL-C were related to an increase in GM density in the left hippocampus, the insular cortex, and the left cerebellar lobule. We also observed exercise-dependent changes of diffusivity parameters in surrounding WM structures as well as in the corpus callosum. These findings suggest that weight-loss due to physical exercise in overweight to obese participants induces profound structural brain plasticity, not primarily of sensorimotor brain regions involved in physical exercise, but of regions previously reported to be structurally affected by an increased body weight and functionally implemented in gustation and cognitive processing.

Obesity-Related Differences between Women and Men in Brain Structure and Goal-Directed Behavior.

Gender differences in the regulation of body-weight are well documented. Here, we assessed obesity-related influences of gender on brain structure as well as performance in the Iowa Gambling Task. This task requires evaluation of both immediate rewards and long-term outcomes and thus mirrors the trade-off between immediate reward from eating and the long-term effect of overeating on body-weight. In women, but not in men, we show that the preference for salient immediate rewards in the face of negative long-term consequences is higher in obese than in lean subjects. In addition, we report structural differences in the left dorsal striatum (i.e., putamen) and right dorsolateral prefrontal cortex for women only. Functionally, both regions are known to play complimentary roles in habitual and goal-directed control of behavior in motivational contexts. For women as well as men, gray matter volume correlates positively with measures of obesity in regions coding the value and saliency of food (i.e., nucleus accumbens, orbitofrontal cortex) as well as in the hypothalamus (i.e., the brain's central homeostatic center). These differences between lean and obese subjects in hedonic and homeostatic control systems may reflect a bias in eating behavior toward energy-intake exceeding the actual homeostatic demand. Although we cannot infer from our results the etiology of the observed structural differences, our results resemble neural and behavioral differences well known from other forms of addiction, however, with marked differences between women and men. These findings are important for designing gender-appropriate treatments of obesity and possibly its recognition as a form of addiction.

Sex-dependent influences of obesity on cerebral white matter investigated by diffusion-tensor imaging.

Several studies have shown that obesity is associated with changes in human brain function and structure. Since women are more susceptible to obesity than men, it seems plausible that neural correlates may also be different. However, this has not been demonstrated so far. To address this issue, we systematically investigated the brain's white matter (WM) structure in 23 lean to obese women (mean age 25.5 y, std 5.1 y; mean body mass index (BMI) 29.5 kg/m(2), std 7.3 kg/m(2)) and 26 lean to obese men (mean age 27.1 y, std 5.0 y; mean BMI 28.8 kg/m(2), std 6.8 kg/m(2)) with diffusion-weighted magnetic resonance imaging (MRI). There was no significant age (p>0.2) or BMI (p>0.7) difference between female and male participants. Using tract-based spatial statistics, we correlated several diffusion parameters including the apparent diffusion coefficient, fractional anisotropy (FA), as well as axial (λ(∥)) and radial diffusivity (λ(⊥)) with BMI and serum leptin levels. In female and male subjects, the putative axon marker λ(∥) was consistently reduced throughout the corpus callosum, particularly in the splenium (r = -0.62, p<0.005). This suggests that obesity may be associated with axonal degeneration. Only in women, the putative myelin marker λ(⊥) significantly increased with increasing BMI (r = 0.57, p<0.005) and serum leptin levels (r = 0.62, p<0.005) predominantly in the genu of the corpus callosum, suggesting additional myelin degeneration. Comparable structural changes were reported for the aging brain, which may point to accelerated aging of WM structure in obese subjects. In conclusion, we demonstrate structural WM changes related to an elevated body weight, but with differences between men and women. Future studies on obesity-related functional and structural brain changes should therefore account for sex-related differences.

Lead poisoning due to adulterated marijuana in leipzig.

BACKGROUND: Between August and December 2007, a mass poisoning due to adulterated marijuana was uncovered in the area of Leipzig, Germany. METHODS: Retrospective reports of patients with lead poisoning who were treated at Leipzig University Hospital. Analysis of data from the local health office, where marijuana consumers could have their blood lead concentration determined. RESULTS: At Leipzig University Hospital, 35 patients (7 female; age 24.2 +/- 4.4 years) had to be treated for lead poisoning (blood lead levels 1063.3 +/- 864.0 microg/L). Five hundred ninety-seven marijuana consumers (439 men, 158 women; age 26.9 +/- 4.8 years) had their blood lead levels measured at the local health office. Among them, 27.3% had lead levels above the HBM-II threshold, 12.2% had concentrations that required monitoring, and 60.5% had levels below the HBM-I threshold. CONCLUSION: Drug consumption should be considered in otherwise unexplained anemia and abdominal colic. Several hundred people suffered lead poisoning presumably resulting from the desire of drug dealers to maximize profits.

Awareness of pathophysiological concepts of type 2 diabetes: a survey in 847 physicians.

AIMS: The aim of the study was to determine physicians' knowledge of specific concepts generally implicated in the pathophysiology of type 2 diabetes (T2D). METHODS: A multiple choice online survey was completed by 847 physicians, of which 516 were engaged in primary care (PCP) and 331 in specialized care (SCP) in the US, the UK, Germany and France (3-30 years in practice, at least 40 patients with T2D). A continuous rating system was used to measure familiarity ("totally familiar" to "never heard of") or agreement with a statement (from "totally agree" to "totally disagree"). RESULTS: The term "insulin resistance" was recognized by 74% of PCPs and 90% of SCPs (p<0.05) and 76% felt that it was "a key but not the sole determinant of T2D". Only 47% agreed that "beta cell dysfunction is a key determinant of T2D onset" and 57% agreed with "beta cell dysfunction being a key determinant of T2D progression". Even among SCPs, 6% were not familiar with the term "beta cell dysfunction" (16% among PCPs, p<0.05). The overall familiarity with the following terms was: 55% with "beta cell dysfunction", 56% with "beta cells", 38% with "glucagon", 32% with "alpha cells", 55% with "hepatic glucose output", 15% with "incretins" and 18% with "GLP-1". SCPs were significantly more familiar with all terms than PCPs (all p-values <0.05). CONCLUSIONS: The pathogenetic role of beta cell dysfunction in the onset and progression of T2D did not seem to be well established. "Insulin resistance" was a well known concept even among PCPs, while "hepatic glucose output", "pancreatic alpha cells" and "glucagon" were not. Incretin hormones and GLP-1 were widely unknown. This may effect prescribing behaviour and how well an individual's therapy is based on pathophysiology.