Fluorine-Terminated Diamond Surfaces as Dense Dipole Lattices: The Electrostatic Origin of Polar Hydrophobicity.

Despite the pronounced polarity of C-F bonds, many fluorinated carbon compounds are hydrophobic: a controversial phenomenon known as "polar hydrophobicity". Here, its underlying microscopic mechanisms are explored by ab initio calculations of fluorinated and hydrogenated diamond (111) surfaces interacting with single water molecules. Gradient- and van der Waals-corrected density functional theory simulations reveal that "polar hydrophobicity" of the fully fluorinated surfaces is caused by a negligible surface/water electrostatic interaction. The densely packed C-F surface dipoles generate a short-range electric field that decays within the core repulsion zone of the surface and hence vanishes in regions accessible by adsorbates. As a result, water physisorption on fully F-terminated surfaces is weak (adsorption energies Ead < 0.1 eV) and dominated by van der Waals interactions. Conversely, the near-surface electric field generated by loosely packed dipoles on mixed F/H-terminated surfaces has a considerably longer range, resulting in a stronger water physisorption (Ead > 0.2 eV) that is dominated by electrostatic interactions. The suppression of electrostatic interactions also holds for perfluorinated molecular carbon compounds, thus explaining the prevalent hydrophobicity of fluorocarbons. In general, densely packed polar terminations do not always lead to short-range electric fields. For example, surfaces with substantial electron density spill-out give rise to electric fields with a much slower decay. However, electronic spill-out is limited in F/H-terminated carbon materials. Therefore, our ab initio results can be reproduced and rationalized by a simple classical point-charge model. Consequently, classical force fields can be used to study the wetting of F/H-terminated diamond, revealing a pronounced correlation between adsorption energies of single H2O molecules and water contact angles.

Selective staining of Brønsted acidity in zeolite ZSM-5-based catalyst extrudates using thiophene as a probe.

Optical absorption and confocal fluorescence micro-spectroscopy were applied to investigate Brønsted acidity in millimetre-sized extrudates of Na(H)-ZSM-5 and SiO2 with varying ZSM-5 content. Partially (residual Na present) and fully proton-exchanged extrudates were employed, using thiophene oligomerization as a probe reaction. Time-resolved in situ optical absorption spectra and time dependent DFT calculations revealed several initial reaction pathways during the oligomerization reaction. In particular, it was found that protonated thiophene monomers reacted by either oligomerization (via reaction with un-reacted thiophene monomers) or ring-opening, depending on the Brønsted acid site density in each sample. Moreover, fully-exchanged extrudates not only have significantly higher reactivity than partially-exchanged samples, but they also favour the formation of ring-opening products, that are not formed on the partially-exchanged samples. Confocal fluorescence microscopy was employed to visualise non-invasively in 3D, the heterogeneity and homogeneity of thiophene oligomers on partially- and fully-exchanged extrudates, respectively. Furthermore, it was observed that extrudates with high binder content produce a higher relative amount of conjugated species, related with a higher quantity of available monomer in the binder, which is able to react further with intermediates adsorbed on active sites. Moreover, these conjugated species appear to form near the external surface of ZSM-5 crystals/agglomerates.

A critical review of classification of organisations in relation to the voluntary implementation of environmental management systems.

The need and ability of an organisation to manage and control its impact on the environment has been hotly debated in recent times. However, the uptake of certificated environmental management systems (EMS), specifically BS EN ISO 14001 (ISO 14001) (British Standards Institution, 2004), is becoming more prevalent, even though evidence of the individual benefits is less clear. Furthermore, reports are often limited and anecdotal in their discussion of the true barriers that organisations experience during the certification and management of their EMS. Presently organisations are commonly classified simply according to size and the barriers they experience when implementing an EMS successfully. This system of classification is not sufficient to understand the multifaceted environments within which modern organisations operate. This paper reviews existing classification methodologies relevant to environmental management so as to determine whether opportunities exist for their practical application in this sector. It begins with an introduction to EMS and existing discussions regarding implementation is provided before a more detailed consideration of organisational size, the integration and development of environmental management within an organisation, then cladistics and quality management systems (QMS) are reviewed as potential opportunities for classification. This shows that whilst numerous methods are available, none function beyond the theoretical, or that the classes provided restrain the description of the complex tasks. Central to differences faced by organisations are insights to the true hurdles that each experience when implementing an EMS. It is shown here how the manipulation of techniques from the more mature field of Energy Management may offer a direction for the development of robust classes. A valuable outcome is that these methods produce classifications that are fit for purpose to better support organisations through the implementation and management of their EMS.

Binder Effects in SiO2- and Al2O3-Bound Zeolite ZSM-5-Based Extrudates as Studied by Microspectroscopy.

Microspectroscopic methods were explored to investigate binder effects occurring in ZSM-5-containing SiO2- and Al2O3-bound millimetre-sized extrudates. Using thiophene as a selective probe for Brønsted acidity, coupled with time-resolved in situ UV/Vis and confocal fluorescence microspectroscopy, variations in reactivity and selectivity between the two distinct binder types were established. It was found that aluminium migration occurs in ZSM-5-containing Al2O3-bound extrudates, forming additional Brønsted acid sites. These sites strongly influence the oligomer selectivity, favouring the formation of thiol-like species (i.e., ring-opened species) in contrast to higher oligomers, predominantly formed on SiO2-bound ZSM-5-containing extrudates. Not only were the location and distribution of these oligomers visualised by 3 D analysis, it was also observed that more conjugated species appeared to grow off the surface of the zeolite ZSM-5 crystals (containing less conjugated species) into the surrounding binder material. Furthermore, a higher binder content resulted in an increasing overall reactivity owing to the greater number of stored thiophene monomers available per Brønsted acid site.

Nonspecific interstitial pneumonia, alveolar proteinosis, and abnormal proprotein trafficking resulting from a spontaneous mutation in the surfactant protein C gene.

Human surfactant protein C (hSP-C(1-197)) is synthesized as a 197 amino acid proprotein and cleaved to a mature 3.7 kD form. Although interstitial lung disease in patients with mutations of the hSP-C gene is becoming increasingly recognized, the mechanisms linking molecular events with clinical pathogenesis are not fully defined. We describe a full-term infant with respiratory insufficiency associated with a spontaneous heterozygous mutation resulting in a substitution of lysine for glutamic acid at position 66 (= E66K) of the proximal hSP-C COOH flanking propeptide. Lung histology and biochemical studies of the index patient (hSP-C(E66K)) revealed nonspecific interstitial pneumonia, increased alveolar total phospholipid lacking phosphatidylglycerol, and increased surfactant protein A. Localization of proSP-C from lung sections prepared from this patient using immunofluorescence and immunogold electron microscopy revealed abnormal proSP-C staining in endosomal-like vesicles of type II cells distinct from SP-B. To evaluate the effect of the E66K substitution on intracellular trafficking of proSP-C, fusion proteins consisting of enhanced green fluorescent protein (EGFP) and hSP-C(1-197) (wild type) or mutant hSP-C(E66K) were generated and transfected into A549 cells. EGFP/hSP-C(1-197) was expressed within CD-63-positive, EEA-1-negative vesicles, whereas EGFP/hSP-C(E66K) localized to EEA-1 positive vesicles. The E66K substitution is representative of a new class of SP-C mutation associated with interstitial lung disease that is diverted from the normal biosynthetic pathway. We propose that, similar to other storage disorders, lung injury results from induction of a toxic gain of function induced by the mutant product that is subject to genetic modifiers and environmental influences.

Chlamydia pneumoniae affect surfactant trafficking and secretion due to changes of type II cell cytoskeleton.

Understanding the surfactant dysfunction by gram-negative bacteria pulmonary infection, the intracellular fate of Chlamydia pneumoniae (Cpn), its interaction with uptake, recycling, and secretion of surfactant and with the cytoskeleton of type II pneumocytes was investigated. Bacteria colocalized with surfactant protein (SP)-A-mediated endocytosed lipid and early endosomes (EEA1- and Rab5-positive) after 3 and 6 h of infection. No specific contact with late endosomes (Rab7- and M6PR-positive), lysosomal, or lamellar body markers (CD63, 3C9) was found after 12 h of infection. In Cpn-infected cells, SP-A-mediated lipid uptake was significantly increased. After SP-A-mediated lipid uptake followed by "re-secretion," 90% of the internalized lipid remained intracellularly. SP-A and lipid did strongly colocalize with early endosomes. Internalized SP-A cannot be resecreted rapidly to plasma membrane, and lipid is not transported toward late endosomes (Rab7- and M6PR-positive) or lamellar bodies (CD63- and 3C9-positive). These results indicate that increased surfactant internalization is caused by an inhibition in intracellular surfactant transport. Accumulation of SP-A-mediated lipid was associated with changes in beta-tubulin. Increases in surfactant secretion were associated with changes in F-actin. We postulate that Cpn infection of type II cells causes changes of the cytoskeleton, and that these effects are associated with alterations in intracellular transport and secretion of surfactant.

Downregulation of the epidermal growth factor receptor by human cytomegalovirus infection in human fetal lung fibroblasts.

Epidermal growth factor plays a key role in late fetal lung development and differentiation as well as in regulating surfactant protein A synthesis, which is involved in innate immunity of the lung. Here we show that human cytomegalovirus (HCMV), a known lung pathogen in connatal and postnatal infection of neonates as well as transplant recipients, completely down-regulates EGF receptor (EGF-R) on the surface of human fetal lung fibroblasts. Inhibition of EGF-R synthesis occurs on the transcriptional rather than on the posttranscriptional level. The effect essentially depends on expression of viral immediate early and/or early genes, as binding of ultraviolet light-inactivated virus to the cells had no effect on EGF-R expression. Furthermore, the anti-HCMV drug ganciclovir, which blocks HCMV DNA replication and late gene expression, cannot overcome HCMV-mediated inhibition of EGF-R, suggesting that immediate early or early gene products may be responsible for down-regulation of EGF-R. Interestingly, the glucocorticoid dexamethasone, which is used for its antiinflammatory action to prevent chronic lung disease in preterm infants, promotes HCMV-associated downregulation of the EGF-R by stimulation of viral gene expression. From these data it can be hypothesized that the pathogenesis of HCMV lung infection involves down-regulation of EGF-R and that congenital HCMV infection may cause retardation in lung maturation and surfactant protein synthesis.