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Chemical recycling of plastic wastes can be a useful complement to mechanical recycling to achieve the required plastics recycling rates and to establish a circular economy that is climate neutral and resource-efficient. Different mixed plastic wastes that are subject to future recycling efforts are studied under uniform conditions of intermediate pyrolysis characterized by a medium heating rate and pyrolysis temperature. Product distributions and selected product properties are determined, and process mass and energy balances are derived. Product yields and compositions are highly dependent on the waste pyrolyzed. The results show that pyrolysis is a suitable process to recover chemical feedstock from various complex mixed plastic wastes.

Die vorliegende uberarbeitete Leitlinie zum Lipodem wurde unter der Federfuhrung der Deutschen Gesellschaft fur Phlebologie (DGP) erstellt und finanziert. Die Inhalte beruhen auf einer systematischen Literaturrecherche und dem Konsens von acht medizinischen Fachgesellschaften und Berufsverbanden. Die Leitlinie beinhaltet Empfehlungen zu Diagnostik und Therapie des Lipodems. Die Diagnose ist dabei auf der Basis von Anamnese und klinischem Befund zu stellen. Charakteristisch ist eine umschriebene, symmetrisch lokalisierte Vermehrung des Unterhautfettgewebes an den Extremitaten mit deutlicher Disproportion zum Stamm. Zusatzlich finden sich Odeme, Hamatomneigung und eine gesteigerte Schmerzhaftigkeit der betroffenen Korperabschnitte. Weitere apparative Untersuchungen sind bisher besonderen Fragestellungen vorbehalten. Die Erkrankung ist chronisch progredient mit individuell unterschiedlichem und nicht vorhersehbarem Verlauf. Die Therapie besteht aus vier Saulen, die individuell kombiniert und an das aktuelle Beschwerdebild angepasst werden sollten: komplexe physikalische Entstauungstherapie (manuelle Lymphdrainage, Kompressionstherapie, Bewegungstherapie, Hautpflege), Liposuktion und plastisch-chirurgische Interventionen, Ernahrung und korperliche Aktivitat sowie ggf. additive Psychotherapie. Operative Masnahmen sind insbesondere dann angezeigt, wenn trotz konsequent durchgefuhrter konservativer Therapie noch Beschwerden bestehen bzw. eine Progredienz des Befundes und/oder der Beschwerden auftritt. Eine begleitend zum Lipodem bestehende morbide Adipositas sollte vor einer Liposuktion therapeutisch angegangen werden.

Summary The present, revised guidelines on lipedema were developed under the auspices of and funded by the German Society of Phlebology (DGP). The recommendations are based on a systematic literature search and the consensus of eight medical societies and working groups. The guidelines contain recommendations with respect to diagnosis and management of lipedema. The diagnosis is established on the basis of medical history and clinical findings. Characteristically, there is a localized, symmetrical increase in subcutaneous adipose tissue in arms and legs that is in marked disproportion to the trunk. Other findings include edema, easy bruising, and increased tenderness. Further diagnostic tests are usually reserved for special cases that require additional workup. Lipedema is a chronic, progressive disorder marked by the individual variability and unpredictability of its clinical course. Treatment consists of four therapeutic mainstays that should be combined as necessary and address current clinical symptoms: complex physical therapy (manual lymphatic drainage, compression therapy, exercise therapy, and skin care), liposuction and plastic surgery, diet, and physical activity, as well as psychotherapy if necessary. Surgical procedures are indicated if – despite thorough conservative treatment – symptoms persist, or if there is progression of clinical findings and/or symptoms. If present, morbid obesity should be therapeutically addressed prior to liposuction.

The anodic C–H amination of aromatic compounds is a powerful and versatile method for the synthesis of aniline derivatives. By using boron-doped diamond (BDD) anodes, a method initially described by Yoshida et al. for electron-rich arenes was expanded to less-activated aromatic systems e.g., simple alkylated benzene derivatives. Anodes based on sp3 carbon seem to be the key for the electrochemical amination reaction. The corresponding primary anilines are obtained in good yields. Despite the cationic intermediates of the electrolytic reaction tert-butyl moieties are tolerated.

Objective Brain damage and ischemia often trigger cortical spreading depression (CSD), which aggravates brain damage. The proinflammatory cytokine tumor necrosis factor (TNF) is significantly upregulated during brain damage, but it is unknown whether TNF influences spreading depression in cerebral cortex in vivo. This question is important because TNF not only furthers inflammatory reactions but might also be neuroprotective. Here we tested the hypothesis that TNF affects CSD, and we explored the direction in which CSD is modified by TNF. Methods CSD, elicited by pressure microinjection of KCl, was recorded in anesthetized rats and mice. TNF was administered locally into a trough, providing local TNF treatment of a cortical area. For further analysis, antibodies to TNF receptor (TNFR) 1 or 2 were applied, or CSD was monitored in TNFR1 and TNFR2 knockout mice. γ-Aminobutyric acid (GABA)A receptors were blocked by bicuculline. Immunohistochemistry localized the cortical expression of TNFR1 and TNFR2. Results Local application of TNF to the cortex reduced dose-dependently the amplitude of CSD. This effect was prevented by blockade or knockout of TNFR2 but not by blockade or knockout of TNFR1. TNFR2 was localized at cortical neurons including parvalbumin-positive inhibitory interneurons, and blockade of GABAA receptors by bicuculline prevented the reduction of CSD amplitudes by TNF. Interpretation We identified a functional link between TNF and CSD. TNF activates TNFR2 in cortical inhibitory interneurons. The resulting release of GABA reduces CSD amplitudes. In this manner, TNF might be neuroprotective in pathological conditions. Ann Neurol 2014;76:43–53

Treatment of allenyl isothiocyanate with a variety of nucleophiles leads to 5-methylthiazoles with a functional group at the 2-position. The same pattern of reactivity is also seen with N-aminophthalimide. In the presence of azide salt, hydrazoic acid, or N,N-disubstituted hydroxylamines, however, allenyl isothiocyanate is converted into bifunctionalized thiazoles. We explain the formation of these products by nucleophilic addition at the isothiocyanato moiety followed by ring closure and an N–N or N–O cleavage reaction to generate short-lived 2-imino-5-methylidenethiazole or 5-methylidenethiazol-2-one. Such intermediates are trapped by addition reactions to give the final heterocyclic compounds. In the case of N,N-disubstituted hydroxylamines, the primary addition products with allenyl isothiocyanate can be detected as unstable intermediates by IR and NMR spectroscopy.

Design guidelines for optimizing the sensing performance of nanoimprinted second order distributed feedback dye lasers are presented. The guidelines are verified by experiments and simulations. The lasers, fabricated by UV-nanoimprint lithography into Pyrromethene doped Ormocomp thin films on glass, have their sensor sensitivity enhanced by a factor of up to five via the evaporation of a titanium dioxide (TiO2) waveguiding layer. The influence of the TiO2 layer thickness on the device sensitivity is analyzed with a simple model that accurately predicts experimentally measured wavelength shifts induced by varied superstrate refractive indices. The superstrate refractive index is additionally shown to determine which of the possible waveguiding modes dominates for lasing, indicating a method to flexibly select the polarization of the laser. The detection limit of the sensor system is further discussed, finding an optimum at 7.5· 10−6 RIU. Wavelength changes caused by dye bleaching must be taken into account for long-term measurements.

The oxy-Cope rearrangement of aldol products has been studied both experimentally and theoretically to gain insight into the aspects that are responsible for the exceptional rate and diastereoselectivity of this process. Kinetic studies as well as DFT calculations convincingly show that the activation barrier of this process is mainly dependent on the electronic nature of the oxy-substituent, with electron-withdrawing O-substituents raising this barrier. The diastereoselectivity, however, remains uniformly high for all derivatives investigated and steric factors are proposed to account for the selectivity to a large extent. The poor diastereoselectivity in the case of the anti-aldols was also found in our calculations and it appears to result from unfavorable gauche interactions between the oxy and carboximide groups in the transition state.

Objective During inflammation in the joint, normal joint movements are usually painful. A neuronal mechanism for this form of mechanical hyperalgesia is the persistent sensitization of joint nociceptors to mechanical stimuli. Because tumor necrosis factor (TNF) is a major mediator of joint inflammation, we undertook the present study both to explore the potential of TNF to sensitize joint nociceptors to mechanical stimuli and to address the cellular mechanism involved. Methods In anesthetized rats, action potentials (APs) were recorded from sensory nociceptive Aδ fibers and C fibers supplying the knee joint. We monitored responses to rotation of the knee joint at innocuous and noxious intensities. TNF, etanercept, and a p38 inhibitor were injected into the knee joint, and the cyclooxygenase (COX) inhibitor diclofenac was administered intraperitoneally. APs were also recorded in isolated cultured dorsal root ganglion (DRG) neurons in order to test for changes in neuronal excitability induced by TNF. Results A single application of TNF into the normal knee joint caused a significant persistent sensitization of nociceptive sensory fibers to mechanical stimuli applied to the joint. This effect was dose dependent. It was prevented by coadministration of etanercept or by an inhibitor of p38, and it was attenuated by systemic application of a COX inhibitor. Patch clamp recordings from isolated DRG neurons showed a rapid increase in neuronal excitability induced by TNF. Conclusion TNF can induce a long-lasting sensitization of joint nociceptors to mechanical stimuli and thus can induce long-lasting mechanical hyperalgesia in joints. TNF can act directly on neurons, underscoring its role as a sensitizing pain mediator.

Methyl cation affinity (MCA) values have been calculated for a variety of phosphanes at the MP2(FC)/6-31+G(2d,p)//B98/6-31G(d) level of theory. The analysis of MCA values for tri-alkyl phosphanes reveals that substituent effects are additive for unbranched and cyclic alkyl substituents, and (with some modification) also for most of the branched alkyl substituents. Copyright © 2010 John Wiley & Sons, Ltd.

The proinflammatory cytokines tumor necrosis factor-alpha (TNF-alpha) and interleukin-6 (IL-6) not only promote and maintain inflammation, they also contribute to the generation and maintenance of inflammatory pain by acting at nociceptive nerve cells. A large proportion of dorsal root ganglion (DRG) neurons express TNF receptors and receptor units for stimulation with IL-6. In the rat model of antigen-induced arthritis (AIA), neutralization of TNF-alpha by etanercept and infliximab reduced inflammation-evoked mechanical hyperalgesia at the inflamed knee joint. This treatment also attenuated the infiltration of macrophages into the DRGs usually observed during the acute phase of AIA. Intra-articular application of etanercept reduced the responses of C-fibers to mechanical stimulation of the inflamed joint but did not influence responses to stimulation of the normal joint. Finally, in cultured DRG neurons TNF-alpha increased the proportion of neurons that express the TRPV1 receptor and may thus contribute to the generation of inflammation-evoked thermal hyperalgesia.

Objective Matrix metalloproteinases (MMPs) have long been considered excellent targets for osteoarthritis (OA) treatment. However, clinical utility of broad-spectrum MMP inhibitors developed for this purpose has been restricted by dose-limiting musculoskeletal side effects observed in humans. This study was undertaken to identify a new class of potent and selective MMP-13 inhibitors that would provide histologic and clinical efficacy without musculoskeletal toxicity. Methods Selectivity assays were developed using catalytic domains of human MMPs. Freshly isolated bovine articular cartilage or human OA cartilage was used in in vitro cartilage degradation assays. The rat model of monoiodoacetate (MIA)–induced OA was implemented for assessing the effects of MMP-13 inhibitors on cartilage degradation and joint pain. The surgical medial meniscus tear model in rats was used to evaluate the chondroprotective ability of MMP-13 inhibitors in a chronic disease model of OA. The rat model of musculoskeletal side effects (MSS) was used to assess whether selective MMP-13 inhibitors have the joint toxicity associated with broad-spectrum MMP inhibitors. Results A number of non–hydroxamic acid–containing compounds that showed a high degree of potency for MMP-13 and selectivity against other MMPs were designed and synthesized. Steady-state kinetics experiments and Lineweaver-Burk plot analysis of rate versus substrate concentration with one such compound, ALS 1-0635, indicated linear, noncompetitive inhibition, and Dixon plot analysis from competition studies with a zinc chelator (acetoxyhydroxamic acid) and ALS 1-0635 demonstrated nonexclusive binding. ALS 1-0635 inhibited bovine articular cartilage degradation in a dose-dependent manner (48.7% and 87.1% at 500 nM and 5,000 nM, respectively) and was effective in inhibiting interleukin-1α– and oncostatin M–induced C1,C2 release in human OA cartilage cultures. ALS 1-0635 modulated cartilage damage in the rat MIA model (mean ± SEM damage score 1.3 ± 0.3, versus 2.2 ± 0.4 in vehicle-treated animals). Most significantly, when treated twice daily with oral ALS 1-0635, rats with surgically induced medial meniscus tear exhibited histologic evidence of chondroprotection and reduced cartilage degeneration, without observable musculoskeletal toxicity. Conclusion The compounds investigated in this study represent a novel class of MMP-13 inhibitors. They are mechanistically distinct from previously reported broad-spectrum MMP inhibitors and do not exhibit the problems previously associated with these inhibitors, including selectivity, poor pharmacokinetics, and MSS liability. MMP-13 inhibitors exert chondroprotective effects and can potentially modulate joint pain, and are, therefore, uniquely suited as potential disease-modifying osteoarthritis drugs.

Ion energy distributions have been measured with an energy-dispersive mass spectrometer during magnetron sputtering of Al doped ZnO. A d.c. and a pulsed d.c. discharge have been investigated. Different positive ions from the target material have been observed with low energies in d.c. and a second energy peak of about 30 eV in pulsed d.c. with only weak additional energy due to the sputter process. Negative ions are mainly O− with energies corresponding to the target voltage of several 100 eV. They originate from the target and barely from the (O2) gas and hit the substrate opposite the race track. In pulsed d.c., due to the varying target voltage, energies of up to 500 eV have been observed. With increasing pressure, negative ions at the substrate are reduced exponentially in their density but not in their energy.

Objective The reduction of pain in the course of antiinflammatory therapy can result from an attenuation of the inflammatory process and/or from the neutralization of endogenous mediators of inflammation that act directly on nociceptive neurons. The purpose of this study was to investigate whether analgesic effects of the neutralization of tumor necrosis factor α (TNFα) are due to an attenuation of inflammation or whether direct neuronal effects significantly contribute to pain relief in the course of therapy. Methods Locomotor and pain-related behavior and histology were assessed in rats with chronic antigen-induced arthritis (AIA) in the knee joint, and the rats were treated with systemic saline, etanercept, or infliximab. The expression of TNF receptors (TNFRs) in dorsal root ganglia was measured using immunohistochemical analysis and polymerase chain reaction. Action potentials were recorded from afferent Aδ fibers and C fibers of the medial knee joint nerve, and etanercept and infliximab were injected intraarticularly into normal or inflamed knee joints (AIA or kaolin/carrageenan-induced inflammation). Results In rats with AIA, both etanercept and infliximab significantly decreased inflammation-induced locomotor and pain-related behavior, while joint swelling was only weakly attenuated and histomorphology still revealed pronounced inflammation. A large proportion of dorsal root ganglion neurons showed TNFRI- and TNFRII-like immunoreactivity. Intraarticular injection of etanercept reduced the responses of joint afferents to mechanical stimulation of the inflamed joint starting 30 minutes after injection, but had no effect on responses to mechanical stimulation of the uninflamed joint. Conclusion Overall, these data show the pronounced antinociceptive effects of TNFα neutralization, thus suggesting that reduction of the effects of TNFα on pain fibers themselves significantly contributes to pain relief.

Eine Grosflachenbeschichtung mit leitfahigen transparenten Schichten erfordert eine homogene Verteilung der Prozessparameter am Substrat. Nachteilig wirken sich hierbei der Cross-Corner-Effekt bei der Einzel-Magnetronquelle sowie der Cross-Magnetron-Effekt beim Dualmagnetron aus. Messungen belegen einen erheblichen Einfluss dieser Effekte auf die laterale Verteilung der Plasmaeigenschaften am Substrat. Es werden die gemessenen funktionellen Eigenschaften von Indium-Zinn-Oxydschichten im Zusammenhang mit der Konzentration des dissoziierten Sauerstoffs im Prozessgas diskutiert, die von den Plasmaeigenschaften und dem Sauerstoffpartialdruck bestimmt wird. Cross Magnetron Effect and ITO Film Deposition The large area deposition of TCO films requires a strictly homogeneous lateral distribution of the process parameters at the substrate position. In view of that, Cross Corner Effect (in case of a single magnetron source) and Cross Magnetron Effect (for dual magnetrons) can cause problems. Measurements confirm a distinct influence of these effects on the functional properties of indium tin oxide films. The effect will be discussed in terms of the concentration of the dissociated oxygen in the process gas, which depends on the plasma properties and the oxygen partial pressure.

Magnetron-sputtered oxide films are widely used for industrial applications. Especially the coating of large substrate areas implies the requirement for reliable and lateral homogeneous film properties. However, the inhomogeneous distribution of the sputter rate as well as cross-corner and cross-magnetron effects may reduce the functional film performance. Therefore, we have investigated the electrical, optical and structural film properties of indium tin oxide (ITO) films in relation to the physical process properties. The films were deposited using a reactive AC dual magnetron discharge and In:Sn targets. For investigation of the influence of the plasma property distribution on film properties static deposition experiments were performed. Substrate temperature measurements have confirmed the inhomogeneous distribution of the plasma properties, resulting from the cross-magnetron effect.

An asymmetric-bipolar pulsed magnetron discharge was spatially studied in two dimensions with a time-resolved Langmuir double probe. The cylindrical magnetron was equipped with an Mg target. The development of the charge carrier density during one pulse reveals the same characteristic as the two-peak structure at the beginning of the ‘on’ phase which we have observed earlier. This temporal peak structure changes with position within the volume of the discharge between target and substrate. While the first maximum is dominant in the discharge centre with the plasma torus of the magnetron only weakly pronounced, the second peak is very intense in the torus region and comparably weak in the whole rest of the discharge. This peak distribution is explained by a simple model based on the acceleration of electrons left over from the previous pulse.

We have investigated the plasma properties of a dual magnetron system used for the deposition of transparent and conductive ITO films. The process properties of a bipolar and unipolar pulsed discharge were investigated while operating the targets in the transition mode. In general, in the bipolar pulsed discharge lower electron temperatures as well as one order of magnitude higher values of charge carrier density were observed compared to the unipolar pulsed discharge. Moreover, strong lateral variations of the charge carrier density in front of the substrate area were found. The influence of the plasma properties on global process parameters, especially on the p–F curve of the transition mode, is discussed in terms of the dissociation of oxygen in the discharge.

Die vor etwa zehn Jahren begonnene Erforschung des Reaktionsverhaltens von Hexahydrotoluylendiisocyanat hatte ein unerwartetes Ergebnis: Die polycyclischen Iminooxadiazindione waren entdeckt. Dabei gewonnene Erkenntnisse fuhrten zu einer neuen Klasse von Hartern fur die Lackindustrie.

Since 1961, aliphatic polyisocyanates based on HDI-biurets are used as light stable hardeners for 2-K polyurethane coatings. The market introduction of the HDI-isocyanurates or simply 'trimers' in the early 1980's was driven by their lower viscosity and their better monomer stability. The most recent development in HDI-polyisocyanate research are the iminooxadiazinediones (asymmetric trimers). In this paper, a new product based on that technology with a very low viscosity (700 mPas@23°C) and a NCO-functionality of more than 3 is presented. Because of its low viscosity, this hardener can be easily incorporated into aqueous systems and is the solution for high and full solids coatings as well.

A solution of sodium in liquid ammonia reacts with Sb2S3 to form large colorless crystals of the composition Na3SbS3⋅10 NH3. The trigonal-pyramidal SbS33− anion is ion-paired with three Na+ counter ions, the coordination spheres of which are completed by eight ammine ligands. The resulting neutral [Na(NH3)3]2[Na(NH3)2]SbS3 molecules crystallize together with two ammonia molecules of solvation in the space group P21/c (a=9.828(2), b=6.0702(4), c=33.4377(6) A, β=91.362(7)°, V=1994.2(5) A3, Z=4).

43 Dr. Nikolaus Nestle, Munchen W issenschaftliches Hauptthema der Physikertagung war die Festkorperphysik. Sie ist bekannterweise eine sehr aufregende, aber auch eine sehr anwendungsorientierte Wissenschaft. Besonders dieser Anwendungsaspekt wurde auch in Hamburg wieder deutlich. Festkorperphysik ist der zahlenmasig groste Teilbereich der modernen Physik. Das ausert sich auch in der grosen Zahl der Studierenden, die sich auf diesem Gebiet betatigen. Zusammen mit der Anwendungsorientierung ergibt dies eine Mixtur, die das Gebiet und die darin arbeitenden jungen Wissenschaftler zu einem „begehrten Sammlerobjekt“ machen und zwar besonders fur jede Art von Unternehmen, die sich mit zukunftsorientierter Technologie im weitesten Sinne befassen. Das reicht von den Chipherstellern, den Unternehmensund Finanzberatern bis hin zu Banken und nicht zuletzt auch den Biotech-Unternehmen, deren Erfolge unter anderem sehr stark auf der Anwendung physikalischer Methoden und Verfahren beruhen. Leider werden wir in den nachsten Jahren nicht annahernd den qualifizierten naturwissenschaftlichen Nachwuchs ausbilden konnen, der von Wirtschaft und Forschung in unserem Lande benotigt wird. Schon jetzt ist es sehr schwierig, genugend qualifizierten Nachwuchs fur unsere Forschergruppen in den Universitaten zu finden – der ja bekannterweise notwendig ist, um auch den Ausbildungsauftrag wahrnehmen zu konnen (Stichwort: Einheit von Forschung und Lehre) – weil die Industrie den Arbeitsmarkt „abraumt“. Die sehr gute Resonanz der Unternehmen auf die Jobborse mit taglich drei Parallelveranstaltungen ist ein deutlicher Beleg fur diesen Sachverhalt. Uber das Programm der Fachverbande hinaus gab es neun fachverbandsubergreifende Symposien, die zumeist von zwei bis drei Fachverbanden getragen wurden: Dynamik von Ummagnetisierungsvorgangen (B. Hillebrands, G. Schonhense) Lasergestutzte Schichtabscheidung und Oberflachenmodifizierung (G. Reise) Neue Transportphanomene – Vom Maxwell-Damon zum Verkehrsstau (P. Hanggi, P. Reimann) Organische Festkorper (K. Leo, N. Karl, M. Sokolowski, W. Brutting) Oxidische Dunnschichten (J. Schubert, B. Holzapfel) Rekonstruktion und Wachstum von III-V-Halbleiteroberflachen (F. Bechstedt) Simulation von Wachstum und Strukturbildung (K. Samwer) Wissenschaftliche Information und Kommunikation der Physik (D. Gorlitz) 30 Jahre Gutzwiller-Spurformel (H. Grabert) Bernhard Kramer Ludwig Schultz

A novel methodology for the evaluation of the response of coated substrates to mechanical contact is presented which is based on the combination of a new theoretical method and high-accuracy indentation experiments using a spherical diamond indenter, The concept may be extended in many respects and will be illustrated here only with few special examples: Using low loads, i.e. staying completely in the elastic region, the elastic parameters of film and substrate can be measured with high accuracy. When the indentation experiments is extended until failure of the coating substrate compound, the full stress and strain fields in three dimensions in the very moment of failure can be calculated. The knowledge of those fields enables one to draw conclusions on the relevant mechanisms. Once the failure mode has been identified, layer systems with optimum resistance to that failure mechanism can be found by theoretical simulations.

Objective: Patients with metastatic hormone-refractory prostate cancer have a poor overall survival rate. Newer agents have shown promise in slowing disease progression but are mostly ineffective in improving the overall survival rate, are toxic, and require intravenous administration. In an attempt to maintain treatment efficacy, but to minimize toxicity and improve ease of use, we conducted a pilot trial of an oral regimen consisting of ketoconazole, hydrocortisone, and cyclophosphamide combination therapy. Materials and Methods: Twenty-seven patients with metastatic hormone-refractory prostate cancer were treated with an oral regimen of ketoconazole, 400 mg tid, and hydrocortisone, 20 mg qam and 10 mg qpm, on Days 1–28. Cyclophosphamide, 100 mg/m2, was added on Days 1–14. Treatment was recycled every 28 days. Progression of disease was defined by a progressively rising prostate specific antigen (PSA) level, new lesions as seen on bone scans, or progression of soft-tissue disease. Patient age ranged from 57 to 87 years. Performance status (PS; Eastern Cooperative Oncology Group scale) was 0–2. Pretreatment PSA values ranged from 5.8 ng/mL to 3400 ng/mL (median 68). Results: Twenty-one (78%) of 27 patients with elevated PSA levels demonstrated a ≥50% decline in PSA level for 3 consecutive months. Of the remaining six patients (22%), two progressed within 3 months, two withdrew from the study due to toxicity, and two responded with 96 months, with a median response duration of 9 months. Twenty-two (81%) of 27 patients experienced no significant toxicity, 4 of 27 patients experienced Grade I–III gastrointestinal toxicity, and 1 of 27 patients experienced Grade III hematologic toxicity. Conclusions: The combination of ketoconazole, hydrocortisone, and cyclophosphamide is a well-tolerated oral regimen for the treatment of patients with metastatic hormone-refractory prostate cancer with significant disease activity, and it warrants further investigation.

The time course of propagation of scotoma and blood flow changes during migraine aura parallels the phenomenon of cortical spreading depression (CSD). It was proposed that CSD generates a sterile neurogenic inflammation in the meninges, which may then lead to the activation or sensitization of nociceptors, thus generating headache. We performed rat experiments in which the effect of CSD on plasma extravasation in the dura mater and on neuronal activity in deep laminae of the trigeminal nucleus was assessed in vivo. CSD did not alter dural plasma extravasation measured by means of bovine serum albumin-coupled flourescein (n = 17 rats) compared to the CSD-free contralateral side. In an in vitro model, the application of KCl to the dura at concentrations extracellularly found during CSD did not alter the release of calcitonin gene-related peptide and prostaglandin E2 from the dura. In 33 rats, neither single CSDs nor a series of CSDs altered ongoing neuronal activity or mechanical and/or thermal sensitivity of the deeply located neurons to stimulation of their receptive fields in the dura mater. These results are at variance with data that showed increased c-Fos labeling in superficial laminae of the trigeminal nucleus following CSD. They do not suggest that CSD initiates migraine headache via neurogenic inflammation.

Whereas 1-organyl-phospholanes and 1-organyl-2,3-dihydro-1H-phospholes catalyze isocyanate oligomerization, the reaction of isocyanates with 1-organyl-2,5-dihydro-1H-phospholes results in the formation of 1,3-dienes and a novel class of P-heterocycles, 1,4,2-diazaphospholidine-3,5-diones. Isothiocyanates and carbodiimides exhibit analogous behavior. The resultant species readily form P-oxides, P-sulfides (see picture), and quaternary onium salts.

The turnover frequencies achieved using γ-valerolactone-based ionic liquids are significantly higher compared to widely used ionic liquids such as [bmim]Cl in the title olefin hydrogenation reactions.

Low-temperature deposited titanium nitride layers exhibiting increased and distorted lattices are subjected to in situ X-ray diffraction investigations at different temperatures. Annealing at about 450 °C leads to a complete lattice relaxation due to diffusion of point defects in the lattice. The activation energy for this diffusion can be calculated to be 1.23 ± 0.07 eV (while the reported activation energy of vacancy diffusion in TiN films is 2.09 eV). This proves that lattice widening and distortion in titanium nitride films deposited by dc magnetron sputtering at temperatures below 200 °C is mainly due to atoms on interstitial sites, and that the density of vacancies is high enough that most of the interstitial atoms find a vacancy to recombine, which leads to the observed relaxation.

A theoretical and experimental analysis of the elastic indentation test (spherical indenter) of coated substrates is performed. An analytic solution of the problem is used to calculate both the deformation of the stresses in the substrate and the thin film. In particular, the stress distribution in the interface between coating and substrate is investigated in detail. The Mises criterion for plastic deformation of special substrate-film conbinations is calculated, too.

Durch Methylierung von Me3SnCH2CH[P(O)(OPr-i)2]2 mittels NaH/MeI erhalt man Me3SnCH2C(Me)[P(O)(OPr−i)2]2 (1), das mit Brom in das Dibromid MeBr2SnCH2C(Me)[P(O)(OPr−i)2]2 (2) uberfuhrt wird. Nach der Rontgenkristallstrukturanalyse ist 2 im Festkorper monomer. Das Zinnatom befindet sich im Zentrum eines verzerrten Oktaeders, in dem der funktionelle Substituent intramolekular als tridentater Ligand in facialer Anordnung koordiniert ist. Die beiden Organoreste sind trans-standig angeordnet (CSnC 155,1°), wahrend sich die Sauerstoff- und Bromatome in cis-Anordnung zueinander befinden. Der Sechsring des aus der Koordination des funktionellen Organorestes am Zinnatom resultierenden bicyclischen Molekulfragmentes von 2 weist Wannenkonformation auf, wahrend die beiden Funfringe in Twist-Konformationen vorliegen. Multikern-NMR- und IR-Daten belegen, das 2 seine Festkorperstruktur auch in unpolaren Losungsmitteln beibehalt. Molecular Structure of 2,2-Bis(diisopropoxyphosphonyl)propyl Methyltin Dibromide By methylation of Me3SnCH2CH[P(O)(OPr−i)2]2 with NaH/MeI Me3SnCH2C(Me)[P(O)(OPr−i)2]2 (1) is obtained, which is converted by bromine into the dibromide MeBr2SnCH2C(Me)[P(O)(OPr−i)2]2 (2). An X-ray crystal structure analysis shows 2 to be monomeric. The tin atom is situated in the centre of a distorted octahedron, in which the functional substituent is intramolecular coordinated as tridentate ligand in a facial mode. The two organo groups are arranged in trans-position (CSnC 155.1°), whereas the oxygen and bromine atoms are orientated cis to each other. The six-membered ring of the bicyclic molecular fragment of 2 which results from the coordination of the functional organo group to the tin atom shows a boat-conformation, whereas the two five-membered rings exist in twist-conformations. Multinuclear n.m.r. and i.r. data show that 2 retains its solid state structure also in nonpolar solvents.

A New Synthesis of 6H-1,3-Thiazines A new method for the synthesis of 1,3-thiazines is described. The addition of nucleophiles to γ-isothiocyanatoallylchlorides (1a-j) leads to functionalisation and subsequent cyclisation (nucleophilic cyclofunctionalisation). Reaction of secondary amines or alcohols under catalysis by tert. amines gives numerous 2-dialkylamino- (3a-w) or 2-alkoxy-6H-1,3-thiazines (4a-p).