Is recreational boating a potential vector for non-indigenous peracarid crustaceans in the Mediterranean Sea? A combined biological and social approach.

Shipping is understood to be a major vector for the introduction and spread of marine non-indigenous species (NIS). However, recreational boating is still unregulated and its influence as vector has not yet been assessed for the Mediterranean Sea, which is the second most popular recreational boating destination worldwide. This is the first large-scale study to examine this by a combined biological (analyzing hull and marina fouling) and social approach (boaters surveys on maintenance habits, travel patterns and awareness), focused on peracarid crustaceans. A surprisingly high number of NIS were found on vessels cruising Mediterranean waters, and species compositions suggest an exchange between marina and vessel assemblages. This means recreational boating presents a risk for NIS spread which should warrant regulation. Results also implied that regionally coordinated management should be supported by effective local-scale-based management in the Mediterranean, which could improve upon with targeted environmental education to solve lack of awareness.

Spectroscopic characterization of omega-substituted biphenylthiolates on gold and their use as substrates for "on-top" siloxane SAM formation.

Self-assembled monolayers (SAMs) of omega-substituted biphenylthiolates (omega-MBP) on gold were characterized by spectral ellipsometry, X-ray photoelectron spectroscopy (XPS), infrared reflection absorption spectroscopy (IRRAS), and vibrational sum frequency generation spectroscopy (VSFG). The vibrational studies of the SAMs were supported by an ab initio frequency analysis at HF/6-31G and BP86/6-31G levels, yielding an assignment of all relevant spectral features in the range from 3500 to 1200 cm(-1). We were able to demonstrate that hydroxy-terminated MBP (HMBP) SAMs are basically featureless in the range of the CH stretching vibrations. Accordingly, the adsorption of a SAM of octadecyltrichlorosilane (OTS) on top of this model surface could be studied. A red shift of the C-O stretching vibration from 1281 to 1264 cm(-1) was observed during the chemisorption of OTS, thus allowing for a quantification of the number of OTS molecules involved in surface binding of OTS, which was found to be about 26% on average.

Self-assembled monolayers of semifluorinated alkaneselenolates on noble metal substrates.

Self-assembled monolayers (SAMs) formed from semifluorinated dialkyldiselenol (CF(3)(CF(2))(5)(CH(2))(2)Se-)(2) (F6H2SeSeH2F6) on polycrystalline Au(111) and Ag(111) were characterized by high-resolution X-ray photoelectron spectroscopy, infrared reflection absorption spectroscopy, near edge X-ray absorption fine structure spectroscopy, scanning tunneling microscopy, and contact angle measurements. The Se-Se linkage of F6H2SeSeH2F6 was found to be cleaved upon the adsorption, followed by the formation of selenolate-metal bond. The resulting F6H2Se SAMs are well-ordered, densely packed, and contamination-free. The packing density of these films is governed by the bulky fluorocarbon part, which exhibits the expected helical conformation. A noncommensurate hexagonal arrangement of the F6H2Se molecules with an average nearest-neighbor spacing of about 5.8 +/- 0.2 A, close to the van der Waals diameter the fluorocarbon chain, was observed on Au(111). The orientation of the fluorocarbon chains in the F6H2Se SAMs does not depend on the substrate-the average tilt angle of these moieties was estimated to be about 21-22 degrees on both Au and Ag.

Self-assembled monolayers of alkaneselenolates on (111) gold and silver.

Self-assembled monolayers (SAMs) formed from didodecyl diselenide (C12SeSeC12) and didodecyl selenide (C12SeC12) on (111) Au and Ag substrates were extensively characterized by several complementary techniques. C12SeSeC12 was found to form contamination-free, densely packed, and well-ordered C12Se SAMs on both substrates, whereas the adsorption of C12SeC12 occurred only on Au and resulted in the formation of a SAM-like C12SeC12 film with a low packing density and a conformational disorder. The properties of the C12Se SAMs were compared with those of dodecanethiolate (C12S) SAMs. The packing density, orientational order, and molecular inclination in C12Se/Au and C12S/Au were found to be very similar. In contrast, C12Se/Ag exhibited significantly lower packing density, a lower degree of the conformational and orientational order, and a larger molecular inclination than C12S/Ag. The results suggest a sp3 bonding configuration for the selenium atom on Au and Ag and indicate a larger corrugation of the headgroup-substrate binding energy surface in C12Se/Ag than in C12S/Ag.

The effect of halogen substitution in self-assembled monolayers of 4-mercaptobiphenyls on noble metal substrates.

Self-assembled monolayers (SAMs) formed from 4'-substituted 4-mercaptobiphenyls X-(C6H4)2SH (X-BPT, with X = I, Cl, and F) on polycrystalline (111) gold and silver substrates have been characterized by synchrotron-based high-resolution X-ray photoelectron spectroscopy and angle-resolved near-edge X-ray absorption fine structure spectroscopy. The X-BPT molecules were found to form highly oriented and densely packed SAMs on both substrates, with a smaller molecular inclination in the case of Ag. The experimental data show clear evidence for the charge transfer between the 4'-substituent and biphenyl moieties with the direction and extent of the transfer depending on the electronegativity of the halogen substituent. At the same time, no direct evidence of the charge transfer between the 4'-substituent and the thiolate group was observed. However, the substitution of the 4'-hydrogen by a halogen atom seems to affect the detailed packing arrangements of the SAM constituents.

Irradiation sensitivity of self-assembled monolayers with an introduced "weak link".

The irradiation sensitivity of n-alkanethiolate SAMs can be enhanced by the incorporation of an irradiation-sensitive functionality as a predetermined breaking point into the alkyl chain. Following this general strategy, several different sulfur-derived functional entities with a variable position in the alkyl chain were tested. In some cases, the incorporation of these entities resulted in a noticeable enhancement of the irradiation-induced desorption (by about 30%), even though the chains were not exclusively cut at the position of the incorporated group, but the scission events related to the "weak links" were just added to those in the alkyl matrix. The position of the incorporated group along the alkyl chain was found to be most essential for its performance as a weak link; the enhancement of irradiation-induced desorption was observed only when the groups were placed close to the SAM-ambient interface.

Self-assembled monolayers of 4-mercaptobiphenyls.

This Account focuses on our systematic studies of the formation and properties of self-assembled monolayers (SAMs) of 4-mercaptobiphenyls on gold surfaces. The key difference between alkanethiolate and biphenyl thiolate SAMs is the rigid pi-character of the latter. The pi-conjugation between the adsorbing thiolate and the substituent at the 4'-position results in a molecular dipole moment that affects the adsorption kinetics as well as the equilibrium structure of mixed SAMs. Due to the lack of conformational disorder in the assembling molecules, these SAMs can serve as stable molecularly engineered model surfaces. Infrared spectroscopy and scanning tunneling microscopy, as well as X-ray and helium diffraction studies, suggest that biphenyl moieties in the SAMs have small tilt angles with respect to the surfaces normal. Finally, the morphology of glycine crystals nucleated and grown on these SAM surfaces depends on the structure of the nucleating glycine layer, which, in turn, depends on the H-bonding of these molecules with the SAM surface.

Olanzapine-induced leukopenia with human leukocyte antigen profiling.

Olanzapine is an atypical antipsychotic medication frequently used in the management of psychotic states. While it has proved to be safe compared to clozapine with regard to haematotoxicity, because it has only been available for a few years, full documentation of its haematological side-effects remains incomplete. We report a case of olanzapine-induced leukopenia with associated neutropenia. Since clozapine-induced haematotoxicity has been associated with characteristic human leukocyte antigen (HLA) groups, HLA typing was determined in this patient. Following failure with typical antipsychotic medication, the patient received 10 mg/day of olanzapine. Three weeks later, he developed fever and a significant decrease in leukocyte count. Olanzapine was immediately discontinued. HLA typing was determined. The white cell count returned to normal and the fever, most probably secondary to the low white cell count, subsided with antibiotic treatment. HLA typing results were: A1 24, B7, B35, DRB1*15, DRB1*11, DRB3*01-03, DRB5*01-02. Olanzapine may induce serious leukopenia and neutropenia. HLA typing in this single patient demonstrated a distinct haplotype compared to that previously observed in clozapine-induced haematoxicity.

Self-assembled monolayers of rigid thiols.

The preparation, structure, properties and applications of self-assembled monolayers (SAMs) of rigid 4-mercapto-biphenyls are briefly reviewed. The rigid character of the biphenyl moiety results in a molecular dipole moment that affects both the adsorption kinetics on gold surfaces, as well as the equilibrium structure of mixed SAMs. Due to repulsive intermolecular interaction, the Langmuir isotherm model does not fit the adsorption kinetics of these biphenyl thiols, and a new Ising model was developed to fit the kinetics data. The equilibrium structures of SAMs and mixed SAMs depend on the polarity of the solution from which they were assembled. Infrared spectroscopy suggests that biphenyl moieties in SAMs on gold have small tilt angles with respect to the surfaces normal. Wetting studies shows that surfaces of these SAMs are stable for months, thus providing stable model surfaces that can be engineered at the molecular level. Such molecular engineering is important for nucleation and growth studies. The morphology of glycine crystals grown on SAM surfaces depends on the structure of the nucleating glycine layer, which, in turn, depends on the H-bonding of these molecules with the SAM surface. Finally, the adhesion of PDMS cross-linked networks to SAM surfaces depends on the concentration of interfacial H-bonding. This non-linear relationship suggests that the polymeric nature of the elastomer results in a collective H-bonding effect.

[Prognostic significance of prostatic carcinoma grading according to Helpap]. / Zur prognostischen Bedeutung des Grading von Prostatakarzinomen nach Helpap.

The prognostic significance of the subgrading system introduced by Helpap was retrospectively examined in 342 prostatic carcinomas, revealing a distinct decrease on survival rate with increasing grade of malignancy: during the first three years following diagnosis 21 per cent of the patients with carcinomas graded as Ib died, while all patients with grade Ia carcinomas were still alive. Thus, according to our results, a clinical observation, but no further surgical treatment is recommended in grade Ia cases. At the time of diagnosis, 54.3 per cent of our cases were at the stages T3 or T4. 15.4 per cent of the carcinomas were incidental. The majority (52 per cent) of these cases had to be graded as Ia or Ib, but only 14.8 per cent of the non-incidental tumors did belong to these prognostically most favourable groups. In summary, the prostate carcinoma grading system introduced by Helpap is characterized by prognostic significance and good reproducibility, and thus should be part of the routine diagnosis of prostate carcinoma.