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Herein we report the synthesis and crystal structures of three light alkali metal salts of the dianion of the polycyclic aromatic hydrocarbon 5,6:11,12-di-o-phenylenetetracene (LDOPT). The compounds are obtained by reaction of LDOPT with an excess of lithium or sodium metal in different O-donor solvents (DME, diglyme) and crystallize as naked, solvated-cation separated dianions exhibiting no interaction between the alkali metal ion and the aromatic π-system of LDOPT. Depending on the aprotic etheral solvent and the hardness of the alkaline metal agent a significant structural perturbation of the conjugated carbon framework of LDOPT is observed resulting in a bowl shaped curvature of the anionic π-perimeter, in contrast to its fully planar neutral state. Reduction of LDOPT with lithium in DME results in the formation of the solvent-separated molecular structure of {[(DME-κ2O)3Li+]2(LDOPT2-)}21 containing naked isolated units of dianionic LDOPT. A similar structural arrangement is observed for the corresponding sodium compound {[(DME-κ2O)3Na+]2(LDOPT2-)}22 in which, however, a lesser curvature of the isolated dianionic ligand skeleton compared to 1 is observed. In contrast to 1 and 2 reduction with sodium in diglyme results in the formation of {[(diglyme-κ3O)2Na+]2(LDOPT2-)}0.53. The deformation of the peripheric phenylene rings of [LDOPT2-] in 3 is not as pronounced as compared to 1 and 2. Nevertheless, molecular structures of 1-3 deviate from full-planarity as observed in the parent neutral LDOPT. No preferential endo- or exo-site coordination of the alkaline metal cations Li+ and Na+ on the curved dianionic π-perimeter is observed.

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Twofold reduction of the title molecule 5,6;11,12-di-o-phenylenetetracene (DOPT) with an excess of metallic rubidium and cesium in the presence of strongly coordinating ethers like 18-crown-6-ether (18C6) and tetraglyme results in the formation of the first Rb(i) triple-decker complex and the first Cs(i) coordination polymer of the so far only sparsely studied polyaromatic planar hydrocarbon DOPT. Both compounds are extremely sensitive towards air and water in solution as well as in the solid state. Both compounds exhibit isomerism within their crystal lattices.

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A design for a unique artificial-hair-cell-type sensor (AHCTS) based entirely on 3D-structured, vertically aligned carbon nanotube (CNT) bundles is introduced. Standard microfabrication techniques were used for the straightforward micro-nano integration of vertically aligned carbon nanotube arrays composed of low-layer multi-walled CNTs (two to six layers). The mechanical properties of the carbon nanotube bundles were intensively characterized with regard to various substrates and CNT morphology, e.g. bundle height. The CNT bundles display excellent flexibility and mechanical stability for lateral bending, showing high tear resistance. The integrated 3D CNT sensor can detect three-dimensional forces using the deflection or compression of a central CNT bundle which changes the contact resistance to the shorter neighboring bundles. The complete sensor system can be fabricated using a single chemical vapor deposition (CVD) process step. Moreover, sophisticated external contacts to the surroundings are not necessary for signal detection. No additional sensors or external bias for signal detection are required. This simplifies the miniaturization and the integration of these nanostructures for future microsystem set-ups. The new nanostructured sensor system exhibits an average sensitivity of 2100 ppm in the linear regime with the relative resistance change per micron (ppm µm(-1)) of the individual CNT bundle tip deflection. Furthermore, experiments have shown highly sensitive piezoresistive behavior with an electrical resistance decrease of up to ∼11% at 50 µm mechanical deflection. The detection sensitivity is as low as 1 µm of deflection, and thus highly comparable with the tactile hair sensors of insects, having typical thresholds on the order of 30-50 µm. The AHCTS can easily be adapted and applied as a flow, tactile or acceleration sensor as well as a vibration sensor. Potential applications of the latter might come up in artificial cochlear systems. In particular, the stable mechanical bending of the sensor up to 90° opens up unique application opportunities.

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Metal implant sensitivity (intolerance) can cause pain, reduced mobility, loosening of the implant and skin rashes. Knowledge of differential diagnoses, histology and appropriate diagnostics are essential for proper diagnosis. To outline typical clinical signs and histology in metal-implant-associated skin lesions we present three exemplary patients from our implant allergy outpatient department and give an overview of the current literature regarding metal implant sensitivity. In patients with a negative patch test the lymphocyte transformation test may reveal metal sensitization. Even "pure" titanium alloys may contain traces of nickel. The histology of implant-associated skin reactions goes from teleangiectatic postimplantation erythema to eczema and vasculitis. Based on the synopsis of history, clinical picture, allergological testing and histology, metal implant sensitivity can be diagnosed more precisely.

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A significant part of human infections is frequently associated with the establishment of biofilms by (opportunistic) pathogens. Due to the increasing number of untreatable biofilms, there is a rising need to develop novel and effective strategies to prevent biofilm formation on surfaces in medical as well as in technical areas. Bacterial initial attachment and adhesion to surfaces followed by biofilm formation is highly influenced by the physical properties of the surfaces. Consequently, changing these properties or applying different nanostructures is an attractive approach to prevent biofilm formation. Here we report on the effect(s) of surface grown and anchored vertically aligned multi walled carbon nanotubes (MWCNT), which have been made wettable by immersion through a graded ethanol series, on biofilm formation of Klebsiella oxytoca, Pseudomonas aeruginosa, and Staphylococcus epidermidis. We evaluated the biofilm formation under continuous flow conditions by confocal laser scanning microscopy and scanning electron microscopy, and demonstrated significant inhibition of biofilm formation of all the different pathogens by MWCNT of different lengths. Furthermore, the anti-adhesive effects of the MWCNT increased with their overall length. The application potential of our findings on surface grown and anchored vertically aligned MWCNT may represent a suitable contact mechanics based approach to prevent biofilm formation on medical devices or technical sensors operating in fluid environments.

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Stable dispersions of tantalum oxide nanoparticles are accessible from solutions of tantalum(V) complexes with a mixed malonato and alkanolato ligand sphere in ethoxyethanol by microwave processing. The malonato ligand is cleaved during decomposition and acetic acid or acetic acid esters are formed as derived from in situ spectroscopic studies. The solubility of the tantalum precursor and the obtained particle size therefrom depend strongly on the type of alkanolato ligand moiety. Dispersions of the molecular complexes possess good film forming properties. Films with low surface roughness can be obtained by spincoating. These exhibited a dielectric constant of about 15 and disruptive strengths above 1.5 MV cm(-1). The electrical measurements indicate that the presence of moisture is detrimental with respect to the dielectric performance of the films. After removal of the solvent from the suspensions of the nanoparticles, the residue can be redispersed in aprotic solvents. The particles can be isolated therefrom by precipitation with pentane. XRD and HRTEM indicate that the material remains amorphous up to temperatures of 750 °C. XPS proved that only Ta2O5 is formed as lower oxidation states of Ta cannot be detected. A detailed EPR study allows us to gain insight into the surface defect chemistry. Multiple types of oxygen vacancies exist at the surface of the Ta2O5 particles which are influenced by additional calcination and annealing in a vacuum.

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Two types of carbon nanotube electrodes (1) buckypaper (BP) and (2) vertically aligned carbon nanotubes (vaCNT) have been used for elaboration of glucose/O2 enzymatic fuel cells exploiting direct electron transfer. For the anode pyrroloquinoline quinone dependent glucose dehydrogenase ((PQQ)GDH) has been immobilized on [poly(3-aminobenzoic acid-co-2-methoxyaniline-5-sulfonic acid), PABMSA]-modified electrodes. For the cathode bilirubin oxidase (BOD) has been immobilized on PQQ-modified electrodes. PABMSA and PQQ act as promoter for enzyme bioelectrocatalysis. The voltammetric characterization of each electrode shows current densities in the range of 0.7-1.3 mA/cm(2). The BP-based fuel cell exhibits maximal power density of about 107 µW/cm(2) (at 490 mV). The vaCNT-based fuel cell achieves a maximal power density of 122 µW/cm(2) (at 540 mV). Even after three days and several runs of load a power density over 110 µW/cm(2) is retained with the second system (10mM glucose). Due to a better power exhibition and an enhanced stability of the vaCNT-based fuel cells they have been studied in human serum samples and a maximal power density of 41 µW/cm(2) (390 mV) can be achieved.

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Nanostructured materials lie at the heart of fundamental advances in efficient energy storage and/or conversion, in which surface processes and transport kinetics play determining roles. This review describes recent developments in the synthesis and characterization of composites which consist of lithium metal phosphates (LiMPO(4), M = Fe, Co, Ni, Mn) coated on nanostructured carbon architectures (unordered and ordered carbon nanotubes, amorphous carbon, carbon foams). The major goal of this review is to highlight new progress in using different three dimensional nanostructured carbon architectures as support for the phosphate based cathode materials (e.g.: LiFePO(4), LiCoPO(4)) of high electronic conductivity to develop lithium batteries with high energy density, high rate capability and excellent cycling stability resulting from their huge surface area and short distance for mass and charge transport.

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We report a simple method for the micro-nano integration of flexible, vertically aligned multiwalled CNT arrays sandwiched between a top and bottom carbon layer via a porous alumina (Al(2)O(3)) template approach. The electromechanical properties of the flexible CNT arrays have been investigated under mechanical stress conditions. First experiments show highly sensitive piezoresistive sensors with a resistance decrease of up to ∼35% and a spatial resolution of <1 mm. The results indicate that these CNT structures can be utilized for tactile sensing components. They also confirm the feasibility of accessing and utilizing nanoscopic CNT bundles via lithographic processing. The method involves room-temperature processing steps and standard microfabrication techniques.

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The catalytic CVD synthesis, using propyne as carbon precursor and Fe(NO3)3 as catalyst precursor inside porous alumina, gives carbon nanotube (CNT) bags in a well-arranged two-dimensional order. The tubes have the morphology of bags or fibers, since they are completely filled with smaller helicoidal CNTs. This morphology has so far not been reported for CNTs. Owing to the dense filling of the outer mother CNTs with small helicoidal CNTs, the resulting CNT fibers appear to be stiff and show no sign of inflation, as sometimes observed with hollow CNTs. The fiber morphology was observed by raster electron microscopy (REM), transmission electron microscopy (TEM), and atomic force microscopy (AFM). The carbon material is graphitic as deduced from spectroscopic studies (X-ray diffraction, Raman and electron energy-loss spectroscopy (EELS)). From Mössbauer studies, the presence of two different oxidation states (Fe0 and FeIII) of the catalyst is proven. Geometric structuring of the template by two different methods has been studied. Inkjet catalyst printing shows that the tubes can be arranged in defined areas by a simple and easily applied technique. Laser-structuring creates grooves of nanotube fibers embedded in the alumina host. This allows the formation of defined architectures in the microm range. Results on hydrogen absorption and field emission properties of the CNT fibers are reported.

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OBJECTIVE: To establish the validity of the Orientation Log (O-Log) by comparison with the Galveston Orientation and Amnesia Test (GOAT). DESIGN: Correlation of daily measures of orientation. SETTING: Acute rehabilitation hospital. SUBJECTS: Sixty-eight inpatients receiving rehabilitation following traumatic brain injury (TBI). PRIMARY MEASURES: The O-Log and GOAT. RESULTS: There was a significant correlation between the GOAT and O-Log (r = .901, P<.001). A cutoff of 25 on the O-Log was found to be comparable with the 75 cutoff on the GOAT. The scales were equivalent in measuring duration of posttraumatic amnesia. CONCLUSIONS: The O-Log is a valid measure of orientation for people with TBI and offers some advantages in administration over the GOAT.

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Mitochondrial heat shock protein 70 (mtHsp70), an important mitochondrial chaperone, is increased in cardiac muscle mitochondria of hyperthyroid rats. To determine the mechanism(s) underlying this increase, we used variations in thyroid status. In Series I, rats were made hyperthyroid by injecting them with 3,3', 5-triiodo-l-thyronine (T(3)) for 5 days, or by treating them with vehicle. In Series II, animals were given 6-n-propyl-2-thiouracil in their drinking water (0.05% w/v) for a period of 32-42 days to make them hypothyroid. During the last 5 days of treatment these animals received injections of either T(3) or vehicle. T(3) treatment resulted in parallel increases in mtHsp70 protein and mRNA levels in a variety of tissues, suggesting transcriptional regulation. However, evidence of tissue-specific post-transcriptional regulation was also apparent. In isolated heart mitochondria, T(3) treatment resulted in a 1.8-fold increase in mtHsp70. This was due to the 1. 6-fold greater import of mtHsp70 into mitochondria in T(3), compared with hypothyroid animals, and it could not be attributed to an altered rate of intramitochondrial mtHsp70 degradation. The rate of processing of mtHsp70 to its mature form, reflecting mitochondrial processing peptidase activity, was unaffected by T(3), but was more rapid than mtHsp70 import. These data indicate a novel mechanism by which T(3) modifies the mitochondrial phenotype via the adaptations in the protein import pathway.

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Iron and titanium oxide nanoparticles have been synthesized in parallel mesopores of alumina by a novel organometallic "chimie douce" approach that uses bis(toluene)iron(0) (1) and bis(toluene)titanium(0) (2) as precursors. These complexes are molecular sources of iron and titanium in a zerovalent atomic state. In the case of 1, core shell iron/iron oxide particles with a strong magnetic coupling between both components, as revealed by magnetic measurements, are formed. Mössbauer data reveal superparamagnetic particle behavior with a distinct particle size distribution that confirms the magnetic measurements. The dependence of the Mössbauer spectra on temperature and particle size is explained by the influence of superparamagnetic relaxation effects. The coexistence of a paramagnetic doublet and a magnetically split component in the spectra is further explained by a distribution in particle size. From Mössbauer parameters the oxide phase can be identified as low-crystallinity ferrihydrite oxide. In agreement with quantum size effects observed in UV-visible studies, TEM measurements determine the size of the particles in the range 5-8 nm. The particles are mainly arranged alongside the pore walls of the alumina template. TiO2 nanoparticles are formed by depositing 2 in mesoporous alumina template. This produces metallic Ti, which is subsequently oxidized to TiO2 (anatase) within the alumina pores. UV-visible studies show a strong quantum confinement effect for these particles. From UV-visible investigations the particle size is determined to be around 2 nm. XPS analysis of the iron- and titania- embedded nanoparticles reveal the presence of Fe2O3 and TiO2 according to experimental binding energies and the experimental line shapes. Ti4+ and Fe3+ are the only oxidation states of the particles which can be determined by this technique. Hydrogen reduction of the iron/iron-oxide nanoparticles at 500 degrees C under flowing H2/N2 produces a catalyst, which is active towards formation of carbon nanotubes by a CVD process. Depending on the reaction conditions, the formation of smaller carbon nanotubes inside the interior of larger carbon nanotubes within the alumina pores can be achieved. This behavior can be understood by means of selectively turning on and off the iron catalyst by adjusting the flow rate of the gaseous carbon precursor in the CVD process.

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The synthesis and structure of heterobimetallic Co/Sn complexes [(eta5-CpR)Co-Sn[CH(SiMe3)2]2] (CpR = C5Me5 2; C5EtMe4 3) are described. Insertion reactions of sulfur and selenium into the unbridged heteronuclear Co-Sn bonds of 1, 2, and 3 (R= H5 1, Me5 2, EtMe4 3) have been studied. Depending on the stoichiometry of the chalcogen element used, novel ternary Sn-chalcogen-Co clusters (8, 9, 15, and 16) can be synthesized, and their molecular structures, which represent rare examples of crystallographically characterized cases of ternary transition metal/chalcogen/tin complexes, have been determined. Electrochemistry shows that complexes 8 and 9 are able to support reversibly either the removal or addition of one electron. Insertion of a further (Cp)Co-E (E = chalcogen) fragment significantly affects the electron distribution and causes complexes 9 and 16 to undergo two consecutive one-electron oxidations. The EPR spectra of the respective monocations have been recorded. In all cases, the unpaired electron strongly interacts with the cobalt nucleus(i), thus testifying that the main contribution to the relevant HOMO orbitals comes from the cobalt atom(s).

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Survivors of traumatic brain injury often have long-term sensory, cognitive and motor deficits that may impair vehicle operation. However, relatively little is known about the driving status and driving characteristics of brain injury survivors. To better understand driving following traumatic brain injury, a survey of driving status, driving exposure, advice received about driving and evaluations of driving competency was administered to a convenience sample of traumatic brain injury survivors (n = 83). The majority of survey participants had experienced either moderate or severe traumatic brain injuries based on the Glasgow Coma Scale. A total of 60% of the survey participants reported that they were currently active drivers. Most individuals (> 60%) who had returned to driving reported driving every day and more than 50 miles per week. Traumatic brain injury survivors frequently received advice about driving from family members, physicians or non-physician health care professionals, but over half (63%) had not been professionally evaluated for driving competency. The presence of high driving exposure, coupled with a lack of widespread driving fitness testing, suggests that some traumatic brain injury survivors have characteristics that may evaluate their risk for vehicle crashes. However, subsequent prospective studies that directly assess driver safety will be needed to confirm this possibility.

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The administration of drugs by subcutaneous infusion is routinely practiced in palliative medicine for the management of patients who are no longer able to take oral medication. It is not uncommon for two or more drugs to be combined in subcutaneous infusion solutions. The combination of an opioid and a short-acting benzodiazepine is frequently required. Unfortunately, the stability of benzodiazepines and newer opioids, such as fentanyl, has not been determined. This study examined the stability of solutions containing either fentanyl alone or fentanyl and midazolam in combination. Eight different solutions were assessed for up to 7 days following preparation. The solutions were prepared in polypropylene syringes using 0.9% saline as a diluent. Duplicate syringes were stored at approximately 5 degrees C, 22 degrees C, and 38 degrees C. High performance liquid chromatography was the analytical technique used to measure fentanyl and midazolam. Initial concentrations ranges were 13.2-38.9 micrograms/mL for fentanyl and 282-959 micrograms/mL for midazolam. It was found that fentanyl (+/- midazolam) was very stable (> 95%) when stored at temperatures ranging from 5 degrees C to 38 degrees C for at least 1 week. Midazolam (+ fentanyl) was not as stable as fentanyl under the same storage conditions and underwent time-dependent decomposition of up to 12.1% (observed at 7 days when stored at 38 degrees C). When stored at 22 degrees C and 38 degrees C, more than 90% of initial midazolam concentrations were retained for 4 days following preparation and for 7 days when stored at 5 degrees C. The clinical implications of these results are that, on the basis of physicochemical stability, subcutaneous infusion solutions containing fentanyl and midazolam may be prepared at intervals of 4 days (or 7 days if stored under refrigerated conditions).

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A method for analyzing flecainide in plasma was developed and assessed. Based on the use of C18 extraction columns eight or fewer times, the rapid and simple extraction procedure provided consistent, high-efficiency flecainide extraction (>85%). Using reverse-phase, high-performance liquid chromatography with fluorometric detection, flecainide acetate was detectable to approximately 15 ng/ml. Retention times of the internal standard and flecainide were 8.9 to 9.2 and 9.8 to 10.4 minutes, respectively, and short sample preparation and run times enabled results to be delivered within 2 to 3 hours of receiving samples. The assay was linear for the standard range 20 ng/ml to 2 microg/ml (r2 with three standards, >0.999) and delivered a high level of accuracy. Quality control concentrations obtained from eight assays consistently fell within 5% of nominal values (100 ng/ml and 1 microg/ml). Based on four assays, the assay was also reproducible with calculated-between and within-assay coefficients of variation of less than 1% and 3%, respectively. The authors found that the performance of this assay was excellent and that the solid-phase extraction technique was simple, rapid, and cost effective.

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OBJECTIVE: To determine if ultrasonography is useful in evaluating penetrating injuries of the trunk to assess whether violation of the peritoneum or pleura has occurred. METHODS: The study group was 29 patients who suffered gunshot (n = 17), stab (n = 10), or shotgun (n = 2) wounds. The abdomen was at risk in 21 injuries, the thorax in eight. The results of physical examination and plain x-rays suggested the pleura and or peritoneum might be intact in all patients. Using a 7-MHz transducer, wound tract(s) were images, looking for the presence of soft-tissue air and/or echolucent areas consistent with soft-tissue blood. Injuries were deemed extraperitoneal or extrapleural if (1) the entire tract was visualized; (2) it appeared superficial to the deepest fascial structure in that area; and (3) in shotgun injuries, all visible pellets on x-ray films were identified by ultrasound in the abdominal wall. RESULTS: Evidence of penetration occurred in four abdominal wounds and one thoracic wound. These were confirmed by operation in the abdominal cases and by subsequent chest x-ray examination in the one thoracic wound. The diagnosis of nonpenetration was confirmed in all the remainder by serial benign abdominal examination (n = 15), chest x-ray examination (n = 8), and laparoscopy (n = 1). Positive and negative predictive accuracy were thus 100% in this pilot series. CONCLUSIONS: Ultrasonographic exploration of penetrating truncal injuries is feasible and accurate. Ultrasonographic wound exploration may serve as a noninvasive and safe replacement for diagnostic laparoscopy, conventional local wound exploration, peritoneal lavage, and 6-hour chest x-rays (repeated chest x-rays taken 6 hours after initial chest x-ray examination). If used as part of the initial physical examination, cost-effectiveness can also be realized.

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Minimally invasive techniques now play an important role in virtually every aspect of general surgery. While it is unlikely that celiotomy for malignant disease will fall into obscurity as rapidly as open cholecystectomy, greater use of videoscopic techniques in surgical oncology are inevitable and will undoubtably improve patient care. Techniques of isopneumic laparoscopy have already proven useful in trauma, cholecystectomy, bowel resection, herniorrhaphy, and a variety of other procedures. Further advances in this technique are dependent on the development of "user friendly" abdominal wall retraction systems.

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Plasma morphine concentrations were measured in five cancer patients receiving long-term epidural morphine administration. Peak concentrations were observed within 1 h of dosage and concentrations then declined biexponentially. Plasma morphine-3-glucuronide (M3G) and morphine-6-glucuronide (M6G) concentrations were measured in two patients and plasma M3G concentrations were observed to be much higher than plasma M6G and morphine concentrations. Peak plasma M6G concentrations occurred within 1.0 h of dosing and plasma M6G concentrations then remained higher than plasma morphine concentrations.

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