Indirect x-ray photodesorption of N215 and CO13 from mixed and layered ices.

X-ray photodesorption yields of N215 and CO13 are derived as a function of the incident photon energy near the N (∼400 eV) and O K-edge (∼500 eV) for pure N215 ice and mixed CO13:N215 ices. The photodesorption spectra from the mixed ices reveal an indirect desorption mechanism for which the desorption of N215 and CO13 is triggered by the photoabsorption of CO13 and N215, respectively. This mechanism is confirmed by the x-ray photodesorption of CO13 from a layered CO13/N215 ice irradiated at 401 eV on the N 1s → π* transition of N215. This latter experiment enables us to quantify the relevant depth involved in the indirect desorption process, which is found to be 30-40 monolayers in that case. This value is further related to the energy transport of Auger electrons emitted from the photoabsorbing N215 molecules that scatter toward the ice surface, inducing the desorption of CO13. The photodesorption yields corrected from the energy that can participate in the desorption process (expressed in molecules desorbed by eV deposited) do not depend on the photon energy; hence, they depend neither on the photoabsorbing molecule nor on its state after Auger decay. This demonstrates that x-ray induced electron stimulated desorption, mediated by Auger scattering, is the dominant process explaining the desorption of N215 and CO13 from the ices studied in this work.

Interfacial water on organic substrates at cryogenic temperatures: hydrogen bonding and quantification in the submonolayer regime.

Water molecules were used to probe the physical and chemical properties of a model hydrophilic organic organized layer. To this end, H2O adsorption on mercaptoundecanoic acid self-assembled monolayers (SAMs) was investigated at the molecular level under ultra-high vacuum by high resolution electron energy loss spectroscopy (HREELS), through the sensitivity of the water OH stretching modes to the molecular environment. The water interfacial layer formation and structure were studied upon deposition at 28 K. A direct sensitive quantification in the submonolayer regime (10-80% of completion) was achieved by the sole measurement of the OH stretching mode frequencies, and the dominant basic (-COO-)/acidic (-COOH) forms of the terminal functions could be probed. The surface densities of the water interfacial layer and the SAM terminal functions were measured independently, and demonstrated to be comparable. This means that the SAM terminal functions provided anchors for water adsorption through two hydrogen bonds and that the SAM acted as a template even at 28 K. Upon annealing at 110 K, the water molecules were observed to form clusters of higher molecular density, dewetting the supporting substrate. Finally, the vanishing of the supporting substrate vibrational signature, due to the masking effect by the deposited water layer, was used to estimate the depth probed by HREELS through water layers to be 11 ± 2 Å.

Breast prosthesis infection and pets: A case report and review of the literature.

INTRODUCTION: Pets are not always the human's best friends, particularly in the presence of comorbidities such as wounds. The following case report describes a Pasteurella multocida infection of a reconstructive breast implant due to a close contact between a cat and its owner. PRESENTATION OF CASE: A 33-year-old woman developed a breast implant infection 13 days after an immediate breast reconstruction following a mastectomy for a multifocal ductal carcinoma. The wound was explored surgically and the implant removed. Culture extracted from fluid around the prosthesis evidenced the presence of P. multocida, a Gram-negative coccobacillus which is present in the oral commensal flora of cats and dogs. CONCLUSION: In the case of breast infection, surgical revision - with or without removal of the implant - is required in order to carry out a meticulous intraoperative cleaning. Antibiotherapy is always necessary in such cases. Particularly when patients presenting comorbidities are concerned, the focus must be put on avoiding close contact of the wound with pets.

DOS and electron attachment effects in the electron-induced vibrational excitation of terphenylthiol SAMs.

Low energy electron scattering on terphenylthiol (TPT, HS-(C6H4)2-C6H5) self-assembled monolayers (SAMs) deposited onto gold was investigated using high resolution electron energy loss spectroscopy (HREELS) by recording specular elastic and inelastic excitation functions. The electron elastic reflectivity could be directly compared to the sample density-of-states (DOS) above vacuum level. A high reflectivity region was observed in the range 7.2-8.6 eV. Inelastic excitation functions were studied to get insights into the mechanisms involved in the excitation of a selection of vibrational modes (dipolar and impact scattering). In particular, a resonant mechanism was observed in the excitation of the stretching mode ν(CC) at 196 meV. The purely resonant contribution to the electron-induced excitation of the stretching modes ν(CH) (379 meV) could be extracted from the overtone excitation. It is located at 7.2 eV above the vacuum level and is characterized by a width of 3.4 eV.

Low-energy electron induced resonant loss of aromaticity: consequences on cross-linking in terphenylthiol SAMs.

Aromatic self-assembled monolayers (SAMs) can be used as negative tone electron resists in functional surface lithographic fabrication. A dense and resistant molecular network is obtained under electron irradiation through the formation of a cross-linked network. The elementary processes and possible mechanisms involved were investigated through the response of a model aromatic SAM, p-terphenylthiol SAM, to low-energy electron (0-10 eV) irradiation. Energy loss spectra as well as vibrational excitation functions were measured using High Resolution Electron Energy Loss Spectroscopy (HREELS). A resonant electron attachment process was identified around 6 eV through associated enhanced excitation probability of the CH stretching modes ν(CH)(ph) at 378 meV. Electron irradiation at 6 eV was observed to induce a peak around 367 meV in the energy loss spectra, attributed to the formation of sp(3)-hybridized CHx groups within the SAM. This partial loss of aromaticity is interpreted to be the result of resonance formation, which relaxes by reorganization and/or CH bond dissociation mechanisms followed by radical chain reactions. These processes may also account for cross-linking induced by electron irradiation of aromatic SAMs in general.

Selective terminal function modification of SAMs driven by low-energy electrons (0-15 eV).

Low-energy electron induced degradation of a model self-assembled monolayer (SAM) of acid terminated alkanethiol was studied under ultra-high vacuum (UHV) conditions at room and low (~40 K) temperatures. Low-energy electron induced chemical modifications of 11-mercaptoundecanoic acid (MUA, HS-(CH2)10-COOH) SAMs deposited on gold were probed in situ as a function of the irradiation energy (<11 eV) by combining two complementary techniques: High Resolution Electron Energy Loss Spectroscopy (HREELS), a surface sensitive vibrational spectroscopy technique, and Electron Stimulated Desorption (ESD) analysis of neutral fragments. The SAM's terminal functions were observed to be selectively damaged at around 1 eV by a resonant electron attachment mechanism, observed to decay by CO, CO2 and H2O formation and desorption. CO2 and H2O were also directly identified at low temperature by vibrational analysis of the irradiated SAMs. At higher irradiation energy, both terminal functions and spacer alkyl chains are damaged upon electron irradiation, by resonant and non-resonant processes.

Low-energy electron scattering on deuterated nanocrystalline diamond films-a model system for understanding the interplay between density-of-states, excitation mechanisms and surface versus lattice contributions.

Electron energy loss spectrum, elastic reflectivity and selected vibrational excitation functions were measured by High Resolution Electron Energy Loss Spectroscopy (HREELS) for deuterated nanocrystalline dc GD CVD diamond films. The electron elastic reflectivity is strongly enhanced at about 13 eV, as a consequence of the second absolute band gap of diamond preserved up to the surface for D-nano-crystallites. The pure bending modes δ(CD(x)) at 88 meV and 107 meV are dominantly excited through the impact mechanism and their vibration excitation functions mimic the electron elastic reflectivity curve. Pure diamond phonon mode ν(CC) can be probed through the resolved fundamental loss located at 152 meV and through the multiple loss located at 300 meV. In addition to the well-known 8 eV resonance, two supplementary resonances located at 4.5 eV and 11.5 eV were identified and clearly resolved for the first time. A comprehensive set of data is now available on low-energy electron scattering at hydride terminated polycrystalline diamond films grown either by HF (microcrystalline) or dc GD (nanocrystalline) chemical vapour deposition. The careful comparison of the vibrational excitation functions for hydrogen/deuterium termination stretching modes ν(sp(3)-CH(x)) and ν(sp(3)-CD(x)), for hydrogen termination bending modes δ(CH(x)) mixed with diamond lattice modes ν(CC), for deuterium termination bending modes δ(CD(x)), and for multiple loss 2ν(CC) demonstrates the close interplay between three characteristics: (i) the density-of-states of the substrate, (ii) the vibrational excitation mechanisms (dipolar and/or impact scattering including resonant scattering) and (iii) the surface versus lattice character of the excited vibrational modes. This work shows clearly that excitation function measurement provides a powerful and sensitive tool to clarify loss attributions, involved excitation mechanisms, and surface versus lattice characters of the excited vibrational modes.

[About an extreme case of giant lymphoedema of the upper limb: ligasure may be useful and a multidisciplinary approach is mandatory]. / À propos d'un cas de lymphœdème géant du membre supérieur : intérêt du Ligasure(®) et importance du traitement multidisciplinaire.

Treatment of giant lymphoedema remains very difficult. The main problem is not only the obtention of early postoperative favorable results but to keep them long-lasting. The available treatment options are numerous and often combined. The indications have to be adapted to the clinical stage of the lesion. Ligasure(®) give us many advantages in the achievement of the surgical resection due to the quality of the lymphostasis that can be obtained and to the very limited thermic lesions caused to tissues. Long lasting postoperative physiotherapy is of first importance. We here describe a case of a giant lymphoedema of the upper limb after axillary lymph node dissection for breast cancer. The first physiotherapy failed, causing a lymphatic decompensation resulting in a lymphoedematous mass of nearly 7kg. The surgical resection with Ligasure(®) associated to drainage and compressive physiotherapy in the long run allows to obtain good results. The late follow-up after 4 years still shows stable results.

Chemistry induced by low-energy electrons in condensed multilayers of ammonia and carbon dioxide.

We have investigated by means of HREEL spectroscopy electron induced reactivity in a binary CO2 : NH3 ice mixture. It was shown that the interaction of low energy electrons (9-20 eV) with such mixtures induces the synthesis of neutral carbamic acid NH2COOH and that flashing the sample at 140 K induces the formation of ammonium carbamate. The products have been assigned by FTIR spectroscopy of a CO2 : NH3 mixture heated from 10 K to 240 K. A mechanism involving dissociation of NH3 molecules into NH2* and H* radicals is proposed to explain the product formation.

Irreversible perforations in vertebral trabeculae?

UNLABELLED: In human cancellous bone, osteoclastic perforations resulting from normal remodeling were generally considered irreversible. In human vertebral samples, examined by backscatter electron microscopy, there was clear evidence of bridging of perforation defects by new bone formation. Hence trabecular perforations may not be irreversible. INTRODUCTION: Preservation of the trabecular bone microarchitecture is essential to maintain its load-bearing capacity and prevent fractures. However, during bone remodeling, the osteoclasts may perforate the platelike trabeculae and disconnect the structure. Large perforations (>100 microm) are generally considered irreversible because there is no surface on which new bone can be laid down. In this work, we investigated the outcome of these perforations on human vertebral cancellous bone. MATERIALS AND METHODS: Using backscatter electron microscopy, we analyzed 264 vertebral bone samples from the thoracic and lumbar spine of nine subjects (44-88 years old). Nine fields (2 x 1.5 mm) were observed on each block. Several bone structural units (BSUs) were visible on a single trabecula, illustrating a dynamic, historical aspect of bone remodeling. A bridge was defined as a single and recent BSU connecting two segments of trabeculae previously separated by osteoclastic resorption. They were counted and measured (length and breadth, microm). RESULTS AND CONCLUSION: We observed 396 bridges over 2376 images. By comparison, we found only 15 microcalluses on the same material. The median length of the bridge was 165 microm (range, 29-869 microm); 86% being longer than 100 microm and 35% longer than 200 microm. Their breadth was 56 microm (range, 6-255 microm), but the thinnest were still in construction. Bridges were found in all nine subjects included in the study, suggesting that it is a common feature of normal vertebral bone remodeling. These observations support the hypothesis that perforation could be repaired by new bone formation, and hence, might not be systematically irreversible.

Cross-link profile of bone collagen correlates with structural organization of trabeculae.

Little is known regarding the mechanisms that govern the structural organization of cancellous bone. In this study, we compare the nature of the collagen in vertebral cancellous bone with the structural organization of its trabecular network. Cylindrical specimens of cancellous bone from vertebrae were obtained from nine autopsy subjects (ages 46-88). In each subject, eight pairs of corresponding samples were obtained from three levels in the spine and three areas within the vertebral body, leading to a total of 68 pairs of samples. The cylinders from one side were used for morphometry and the classical morphometrical parameters were obtained (BV/TV, bone volume fraction; Tb.Th, trabecular thickness; Tb.N, number; Tb.Sp, trabecular spacing) and strut analysis (TSL, total strut length; Nd, number of nodes; Fe, number of free-ends). The amount of osteoid bone was also quantified. The cylinders from the other side were powdered and used for collagen assessment, including the amount of collagen (% w/w), and its content in immature cross-links; such as hydroxylysinonorleucine (mol/mol of collagen) and dihydroxylysinornorleucine, as well as stable mature cross-links, such as hydroxylysylpyridinoline (HP), lysylpyridinoline (LP), and the pyrrole cross-links. A random regression model was used to explore the correlations. None of the biochemical parameters correlated with the BV/TV except the ratio between immature and mature cross-links (eta(2) = 0.34, p < 0.05). There was no relationship between the amount of osteoid bone and the cross-link profile. However, the concentration of pyrrole and HP cross-links in the bone samples correlated with the structural organization of its trabeculae, but in an opposite direction. Hence, the pyrrole/HP ratio was a good predictor of Tb.Th, Tb.N, Tb.Sp, and TSL (eta(2) > 0.65 and p < 0.01) as well as Fe and star marrow space (eta(2) > 0.45 and p < 0.05). The cylinders from subjects with high pyrrole or low HP in their bone collagen had a relatively thick and simple structure. Those with low pyrrole and high HP had relatively thin trabeculae that were more numerous and spread over a complex network. The relative concentrations of the pyrrole and pyridinoline cross-links appear to reflect the structural organization of the trabeculae.

Vector correlations in dissociative photoionization of diatomic molecules in the VUV range: strong anisotropies in electron emission from spatially oriented NO molecules.

Imaging and time-resolved coincidence techniques are combined to determine ion-electron (v-->(i),v-->(e)) velocity correlations in dissociative photoionization of diatomic molecules induced by synchrotron linearly polarized light P-->. The (v-->(i),v-->(e), P-->) vector correlation yields the identification of each process, together with the ( straight theta(e), straight phi(e)) electron emission in the molecule frame for each orientation of the internuclear axis with respect to the polarization. Strong electron emission anisotropies are observed in the NO molecule frame for the parallel and the perpendicular transitions of the NO+hnu(22-25 eV)-->NO+(c(3) Pi)+e-->N+(3P)+O(3P)+e reaction.