Dielectric Properties of Nanoconfined Water: A Canonical Thermopotentiostat Approach.

We introduce a novel approach to sample the canonical ensemble at constant temperature and applied electric potential. Our approach can be straightforwardly implemented into any density-functional theory code. Using thermopotentiostat molecular dynamics simulations allows us to compute the dielectric constant of nanoconfined water without any assumptions for the dielectric volume. Compared to the commonly used approach of calculating dielectric properties from polarization fluctuations, our thermopotentiostat technique reduces the required computational time by 2 orders of magnitude.

Strong intermolecular antiferromagnetic verdazyl-verdazyl coupling in the solid state.

Strong magnetic couplings are generally observed intramolecularly in organic diradicals or in systems in which they are promoted by crystal engineering strategies involving, for example, transition metal ligation. We herein present a strong intermolecularly coupling verdazyl radical in the solid state without the use of such design strategies. The crystal structure of an acetylene-substituted verdazyl radical shows a unique antiparallel face-to-face orientation of the neighboring verdazyl molecules along with verdazyl-acetylene interactions giving rise to an alternating antiferromagnetic Heisenberg chain. Single crystal structural data at 80, 100, 173, and 223 K show that one of the π-stacking distances depends on temperature, while heat capacity data indicate the absence of a phase transition. Based on this structural input, broken symmetry DFT calculations predict a change from an alternating linear Heisenberg chain with two comparable coupling constants J1 and J2 at higher temperatures towards dominant pair interactions at lower temperatures. The predicted antiferromagnetic coupling is confirmed experimentally by magnetic susceptibility, solid-state EPR and NMR spectroscopic results.

Ab initio Prediction of Martensitic and Intermartensitic Phase Boundaries in Ni-Mn-Ga.

Despite the importance of martensitic transformations of Ni-Mn-Ga Heusler alloys for their magnetocaloric and shape-memory properties, the martensitic part of their phase diagrams is not well determined. Using an ab initio approach that includes the interplay of lattice and vibrational degrees of freedom we identify an intermartensitic transformation between a modulated and a nonmodulated phase as a function of excess Ni and Mn content. Based on an evaluation of the theoretical findings and experimental x-ray diffraction data for Mn-rich alloys, we are able to predict the phase diagram for Ni-rich alloys. In contrast to other mechanisms discussed for various material systems in the literature, we herewith show that the intermartensitic transformation can be understood solely using thermodynamic concepts.

Understanding Anharmonicity in fcc Materials: From its Origin to ab initio Strategies beyond the Quasiharmonic Approximation.

We derive the Gibbs energy including the anharmonic contribution due to phonon-phonon interactions for an extensive set of unary fcc metals (Al, Ag, Au, Cu, Ir, Ni, Pb, Pd, Pt, Rh) by combining density-functional-theory (DFT) calculations with efficient statistical sampling approaches. We show that the anharmonicity of the macroscopic system can be traced back to the anharmonicity in local pairwise interactions. Using this insight, we derive and benchmark a highly efficient approach which allows the computation of anharmonic contributions using a few T=0 K DFT calculations only.

Temperature dependent magnon-phonon coupling in bcc Fe from theory and experiment.

An ab initio based framework for quantitatively assessing the phonon contribution due to magnon-phonon interactions and lattice expansion is developed. The theoretical results for bcc Fe are in very good agreement with high-quality phonon frequency measurements. For some phonon branches, the magnon-phonon interaction is an order of magnitude larger than the phonon shift due to lattice expansion, demonstrating the strong impact of magnetic short-range order even significantly above the Curie temperature. The framework closes the previous simulation gap between the ferro- and paramagnetic limits.

Blocking growth by an electrically active subsurface layer: the effect of Si as an antisurfactant in the growth of GaN.

Combining aberration corrected high resolution transmission electron microscopy and density functional theory calculations we propose an explanation of the antisurfactant effect of Si in GaN growth. We identify the atomic structure of a Si delta-doped layer (commonly called SiN(x) mask) as a SiGaN(3) monolayer that resembles a √3×√3 R30° surface reconstruction containing one Si atom, one Ga atom, and a Ga vacancy (V(Ga)) in its unit cell. Our density functional theory calculations show that GaN growth on top of this SiGaN(3) layer is inhibited by forming an energetically unfavorable electrical dipole moment that increases with layer thickness and that is caused by charge transfer between cation dangling bonds at the surface to V(Ga) bound at subsurface sites.

CAD/CAM-produced surgical guides: Optimizing the treatment workflow.

The increased availability of devices for 3D radiological diagnosis allows the more frequent use of CAD/CAM-produced surgical guides for implant placement. The conventional workflow requires a complex logistic chain which is time-consuming and costly. In a pilot study, the workflow of directly milled surgical guides was evaluated. These surgical guides were designed based on the fusion of an optical impression and the radiological data. The clinical use showed that the surgical guides could be accurately placed on the residual dentition without tipping movements. The conventional surgical guides were used as a control for the manual check of the deviation of the implant axis. The direct transfer of the digital planning data allows the fabrication of surgical guides in an external center without the need of physical transport, which reduces the logistic effort and expense of the central fabrication of surgical guides.

Femtosecond spectroscopy on the photochemistry of ortho-nitrotoluene.

The photo tautomerisations of ortho-nitrotoluene (oNT) and its methylated derivative ortho-ethylnitrobenzene (oENB) have been studied by means of femtosecond spectroscopy and (TD)-DFT computations. In UV/Vis transient absorption spectroscopy a band peaking at 400 nm is seen to rise in a bi-modal manner with time constants of 1-10 ps and 1500 ps. Femtosecond stimulated Raman experiments clearly identify aci-nitro forms as the spectroscopic carriers of the 400 nm band. The assignment of the Raman spectra is based on TD-DFT computations. The quantum yields of the aci-nitro forms after 3 ns are 0.08 (oNT) and 0.3 (oENB). The aci-nitro forms are formed via a singlet channel (1-10 ps) and a triplet channel (1500 ps). There are indications that the triplet channel involves a bi-radical intermediate. In between 3 ns and 1 ms the spectrum of the aci-nitro form shifts from 400 to 390 nm. This could indicate a tautomerisation from Z-aci-nitro to an E form.

Role of hole confinement in the recombination properties of InGaN quantum structures.

We study the isolated contribution of hole localization for well-known charge carrier recombination properties observed in conventional, polar InGaN quantum wells (QWs). This involves the interplay of charge carrier localization and non-radiative transitions, a non-exponential decay of the emission and a specific temperature dependence of the emission, denoted as "s-shape". We investigate two dimensional In0.25Ga0.75N QWs of single monolayer (ML) thickness, stacked in a superlattice with GaN barriers of 6, 12, 25 and 50 MLs. Our results are based on scanning and high-resolution transmission electron microscopy (STEM and HR-TEM), continuous-wave (CW) and time-resolved photoluminescence (TRPL) measurements as well as density functional theory (DFT) calculations. We show that the recombination processes in our structures are not affected by polarization fields and electron localization. Nevertheless, we observe all the aforementioned recombination properties typically found in standard polar InGaN quantum wells. Via decreasing the GaN barrier width to 6 MLs and below, the localization of holes in our QWs is strongly reduced. This enhances the influence of non-radiative recombination, resulting in a decreased lifetime of the emission, a weaker spectral dependence of the decay time and a reduced s-shape of the emission peak. These findings suggest that single exponential decay observed in non-polar QWs might be related to an increasing influence of non-radiative transitions.

The prognostic relevance of lymph node ratio in patients with oral squamous cell carcinoma treated with neoadjuvant therapy regimen and radical surgery.

BACKGROUND: This study aims at investigating the prognostic significance of lymph node ratio (LNR) in a cohort of patients with oral squamous cell carcinomas (OSCC), treated with neoadjuvant radiochemotherapy followed by radical surgery. METHODS: The study included 171 treatment-naive patients with biopsy-proven primary OSCC, being reviewed retrospectively. All patients received a concomitant neoadjuvant radiochemotherapy (RCT) followed by radical surgery of the primary tumor and neck dissection based on the pretreatment staging results. The Kaplan-Meier survival analysis method was used to estimate the events of interest for overall survival (OS). Prognostic factors were identified through univariate and multivariate analysis. RESULTS: The 5-year overall survival rate for all patients was 48 %. In univariate analysis, patient's age and data compiled from the histopathological examination as margin status, extracapsular spread, ypT, ypN, ypUICC, number of positive lymph nodes and lymph node ratio (LNR) had a statistically significant impact on overall survival. Multivariate analysis revealed an independent significant impact of patient age, ypT, margin status and LNR on OS. ypN showed no statistical significant impact on OS. CONCLUSION: Our results show that LNR is an important predictor for OS in patients with OSCC that were treated with neoadjuvant radiochemotherapy and radical surgery.

Intraoperative navigation in the maxillofacial area based on 3D imaging obtained by a cone-beam device.

The aim of this study was to evaluate intraoperative navigation in the maxillofacial area based on three-dimensional imaging obtained by a cone-beam device. Digital volume tomograms (DVT) were obtained by the prototype of GALILEOS (Sirona Dental Systems Inc., Bensheim, Germany), a newly developed, compact size, cone-beam machine with a scan volume of 15 cm x 15 cm x 15 cm. Intraoperative navigation was performed in 12 patients in three selected indications. Target detection error expressing the accuracy of DVT navigation and registration performance of specially developed methods for image-to-patient registration was estimated. Target detection error was maximally 2 mm and depended on the registration method chosen. The automatic detection rate of the fiducial markers ranged between 0.64 and 0.32. The preoperatively defined treatment plan was fully accomplished in 11 out of 12 cases. A favourable surgical outcome was achievable in all cases. Intraoperative complications were not observed. Intraoperative navigation based on DVT imaging can be considered as a valuable alternative to CT-based procedures. Special characteristics of the cone-beam technique, in terms of contrast resolution and the limited field-of-view size of the devices, restrict the indication spectrum and create a demand for modifications of the usual registration methods.

A rare-earth free magnesium alloy with improved intrinsic ductility.

Metals are the backbone of manufacturing owing to their strength and formability. Compared to polymers they have high mass density. There is, however, one exception: magnesium. It has a density of only 1.7 g/cm3, making it the lightest structural material, 4.5 times lighter than steels, 1.7 times lighter than aluminum, and even slightly lighter than carbon fibers. Yet, the widespread use of magnesium is hampered by its intrinsic brittleness. While other metallic alloys have multiple dislocation slip systems, enabling their well-known ductility, the hexagonal lattice of magnesium offers insufficient modes of deformation, rendering it intrinsically brittle. We have developed a quantum-mechanically derived treasure map which screens solid solution combinations with electronic bonding, structure and volume descriptors for similarity to the ductile magnesium-rare earth alloys. Using this insight we synthesized a surprisingly simple, compositionally lean, low-cost and industry-compatible new alloy which is over 4 times more ductile and 40% stronger than pure magnesium. The alloy contains 1 wt.% aluminum and 0.1 wt.% calcium, two inexpensive elements which are compatible with downstream recycling constraints.

The HER2 phenotype of circulating tumor cells in HER2-positive early breast cancer: A translational research project of a prospective randomized phase III trial.

BACKGROUND: HER2 is one of the predominant therapeutic targets in breast cancer. The metastatic selection process may lead to discrepancies between the HER2 status of the primary tumor and circulating tumor cells (CTCs). This study analyzed the HER2 status of CTCs in patients with HER2-positive primary breast cancer at the time of diagnosis. Aim of the study was to assess potential discordance of HER2 status between primary tumor and CTCs, as this may have important implications for the use of HER2-targeted therapy. METHODS: The number and HER2 status of CTCs out of 30ml peripheral blood were assessed in 642 patients using the CellSearch System (Janssen Diagnostics, USA). The cutoff for CTC positivity was the presence of at least 1 CTC, and the cutoff for HER2 positivity of CTCs was the presence of at least 1 CTC with a strong HER2 staining. RESULTS: 258 (40.2%) of the 642 patients were positive for CTCs (median 2; range 1-1,689). 149 (57.8%) of these 258 patients had at least 1 CTC with strong HER2 staining. The presence of HER2-positive CTCs was not associated with tumor size (p = 0.335), histopathological grading (p = 0.976), hormone receptor status (ER: p = 0.626, PR: p = 0.263) or axillary lymph node involvement (p = 0.430). Overall, 83 (32.2%) of the CTC-positive patients exclusively had CTCs with strong HER2 staining, whereas 31 (12.0%) had only CTCs with negative HER2 staining. Within-sample variation in the HER2 status of CTCs was found in 86 (57.8%) of the 149 patients with more than 1 CTC. CONCLUSION: This study demonstrated that discordance between the HER2 expression of CTCs and that of the primary tumor frequently occurs in early breast cancer. Future follow-up evaluation will assess whether this discrepancy may contribute to trastuzumab resistance.

Lateral femoral cutaneous nerve and iliac crest bone grafts--anatomical and clinical considerations.

This study investigates the topographical relationship of the lateral femoral cutaneous nerve (LFCN) to the anterior iliac crest and its clinical relevance in the context of bone graft harvesting. In the anatomical part of the study, LFCN was dissected and its course investigated in 34 human formalin-embalmed cadavers. In the clinical part, data of patients who underwent an iliac crest bone grafting procedure were collected and analysed. The obtained results were then compared with the results of other investigators published in the medical literature. From 34 nerves, the lateral branch of 1 LFCN (2.9%) crossed the anterosuperior iliac spine (ASIS) prominence at a distance less than 5mm superolaterally from the most anterior point of the spine. All other nerves ran below the inguinal ligament with an average distance of 14.6mm in the inferomedial direction from the spine. In 4 out of 298 patients (1.3%) who underwent harvesting of monocortical bone grafts from the inner table of the ilium, sensory disturbances in the dermatome of LFCN were observed. After a maximum period of 12 months all sensory disturbances resolved so that no case of permanent sensory impairment was recorded. The relatively low incidences of iatrogenic LFCN damage can be attributed to a standardized surgical concept which employs a lateral incision and layer by layer dissection to the periosteum/iliacal fascia level in order to identify the nerves potentially crossing the iliac crest above the ASIS.

Comparison of static and dynamic computer-assisted guidance methods in implantology.

The planning of dental implant position and its transfer to the operation site can be considered as one of the most important factors for the long-term success of implant-supported prosthetic and epithetic restorations. This study compares computer-assisted fabricated surgical templates as the static method with intro-operative image guided navigation as the dynamic method for transfer of three-dimensional pre-operative planning. For the static method, the systems Med3D, coDiagnostix/ gonyX, and SimPlant were used. For the dynamic method, the systems RoboDent und VectorVision2 were applied. A total of 746 implants were inserted between August 1999 and December 2005 in 206 patients. The static approach was used most frequently, accounting for 611 fixtures in 168 patients. The failure ratios within the first 6 months were 1.31% in the statically controlled insertion group compared to 2.96% in the dynamically controlled insertion group. Complications related to an incorrect position of the implants have not been observed so far in either group. All computer-assisted methods included in this study were successfully applied in a clinical setting after a certain start-up period. The indications for application of computer-assisted methods in implantology are currently given in difficult anatomical situations. Due to uncomplicated handling and low resource demands, the static template technique can be recommended as the method of choice for the majority of all cases falling into this category.

The impact of carbon and oxygen in alpha-titanium: ab initio study of solution enthalpies and grain boundary segregation.

The solution, grain boundary (GB) segregation, and co-segregation of carbon and oxygen atoms in α-titanium are studied using density functional theory. For five titanium tilt boundaries, including T1, T2, and C1 twin systems, we determine the GB structure, as well as GB energy and excess volume. The segregation energies and volumes of carbon and oxygen are calculated for 23 inequivalent interstitial voids, while for co-segregation 75 configurations are considered. It is obtained that depending on the type of the segregation void both a positive and a negative segregation process is possible. The physical reasons of segregation are explained in terms of the analysis of the void atomic geometry, excess volume and features of the electronic structure at the Fermi level. Although carbon and oxygen show qualitatively similar properties in α-Ti, several distinctions are observed for their segregation behavior and mutual interactions.

Spontaneous formation of indium-rich nanostructures on InGaN(0001) surfaces

InGaN(0001) surfaces prepared by molecular beam epitaxy have been studied using scanning tunneling microscopy and first-principles total energy calculations. Nanometer-size surface structures are observed consisting of either vacancy islands or ordered vacancy rows. The spontaneous formation of these structures is shown to be driven by significant strain in the surface layers and by the relative weakness of the In-N bond compared to Ga-N. Theory indicates that In will preferentially bind at the edges and interior of the structures, thereby giving rise to an inhomogeneous In distribution at the surface.

Analysis of betamethasone in rat plasma using automated solid-phase extraction coupled with liquid chromatography-tandem mass spectrometry. Determination of plasma concentrations in rat following oral and intravenous administration.

A method is described for the determination of betamethasone in rat plasma by liquid chromatography-tandem mass spectrometry (LC-MS-MS). The analyte was recovered from plasma by solid-phase extraction and subsequently analyzed by LC-MS-MS. A Packard Multiprobe II, an automated liquid handling system, was employed for the preparation and extraction of a 96-well plate containing unknown plasma samples, standards and quality control samples in an automated fashion. Prednisolone, a structurally related steroid, was used as an internal standard. Using the described approach, a limit of quantitation of 2 ng/ml was achieved with a 50 microl aliquot of rat plasma. The described level of sensitivity allowed the determination of betamethasone concentrations and subsequent measurement of kinetic parameters of betamethasone in rat. Combination of automated plasma extraction and the sensitivity and selectivity of LC-MS-MS offers a valuable alternative to the methodologies currently used for the quantitation of steroids in biological fluids.

Bone condensing in the placement of endosteal palatal implants: a case report.

Bone condensing as a technique to prepare an implant site is demonstrated on a patient who was to undergo orthodontic treatment utilizing a palatal implant as an anchor. Based on the anatomic constraints of the palate and the desire to load the implant as axially as possible, adapted-instrumentation for bone condensing is presented. Bone condensing for preparation of the implant site in soft maxillary bone avoids the risk of heat generation, and palatal implants can be placed precisely with primary stability.

Survival rates after reconstructions in the aorto-iliac region.

During a twelve year period, 849 patients were operated on because of atherosclerotic diseases in the aorto-iliac region. 31 patients died postoperatively and 48 patients could not be followed up so that the fate of 770 patients is known. These 770 operated patients showed survival rates like a 12 year older normal population. By comparing the survival rates of the operated patients in different age groups, it is concluded that atherosclerotic diseases have an especially bad outcome in younger patients.