High pressure surface plasmon spectroscopy

Der Einfluß von Druck auf die Eigenschaften dünner dielektrischer Filme wurde mit Hilfe von Oberflächenplasmonen-Spektroskopie untersucht. Die Arbeit kann aus der Perspektive der Materialcharakterisierung und aus apparativer Sicht betrachtet werden, da z.B. eine neue Hochdruckzelle konstruiert wurde, die kombinierte Oberflächenplasmonen-Elektrochemie Messungen erlaubt. SiO2-Solgel Filme wurden optimiert und auf ihre Widerstandsfähigkeit in Bufferlösungen und ihre Oberflächeneigenschaften hin untersucht. Eine Anwendung lag in der Charakterisierung von thermoresponsiven Acrylsäureisopropylamid Hydrogelen, die einen Volumenphasenübergang aufwiesen, dessen Eigenschaften durch Druck und die Beschränktheit des Films auf die Oberfläche beeinflußt wurden.Die Charakterisierung von DNA Hybridisierungsreaktionen an Oberflächen wurde mit einer Fluoreszenz-erweiterten Hochdruckapparatur durchgeführt. Zunächst wurde die Stabilität der zugrundeliegenden Bindematrix sichergestellt. Bei DNA Einzelsträngen führten Temperatur und Druck zu jeweils verringertem bzw. erhöhtem Signal. Entropie und Änderungen der Lösungsmitteleigenschaften wurden für die Signaländerungen verantwortlich gemacht. Die Eigenschaften der Doppelhelix wurden im Langmuir-Bild beschrieben. Der Brechungsindex von Kohlendioxid wurde bis zu 200 MPa gemessen und mit vorhandenen Gleichungen verglichen. Weiterhin wurde das Schwellverhalten von PMMA in scCO2/MMA-Mischungen untersucht. Mit Druck und MMA-Konzentration nimmt das Polymer vermehrt Kohlendioxid auf. Dadurch schwillt es an und sein Brechungsindex nimmt ab. Berechnungen unter Annahme einer idealen Mixtur ergaben gute qualitative Übereinstimmung mit den Meßwerten.Abschließend wurde eine neue Elektrochemie-Hochdruckzelle vorgestellt, die an Kaliumhexacyanoferrat(III)-(II) getestet wurde. Die Elektropolymerisation von Thiophen optisch untersucht.

Neurostimulation for Parkinson's disease with early motor complications.

BACKGROUND Subthalamic stimulation reduces motor disability and improves quality of life in patients with advanced Parkinson's disease who have severe levodopa-induced motor complications. We hypothesized that neurostimulation would be beneficial at an earlier stage of Parkinson's disease. METHODS In this 2-year trial, we randomly assigned 251 patients with Parkinson's disease and early motor complications (mean age, 52 years; mean duration of disease, 7.5 years) to undergo neurostimulation plus medical therapy or medical therapy alone. The primary end point was quality of life, as assessed with the use of the Parkinson's Disease Questionnaire (PDQ-39) summary index (with scores ranging from 0 to 100 and higher scores indicating worse function). Major secondary outcomes included parkinsonian motor disability, activities of daily living, levodopa-induced motor complications (as assessed with the use of the Unified Parkinson's Disease Rating Scale, parts III, II, and IV, respectively), and time with good mobility and no dyskinesia. RESULTS For the primary outcome of quality of life, the mean score for the neurostimulation group improved by 7.8 points, and that for the medical-therapy group worsened by 0.2 points (between-group difference in mean change from baseline to 2 years, 8.0 points; P=0.002). Neurostimulation was superior to medical therapy with respect to motor disability (P<0.001), activities of daily living (P<0.001), levodopa-induced motor complications (P<0.001), and time with good mobility and no dyskinesia (P=0.01). Serious adverse events occurred in 54.8% of the patients in the neurostimulation group and in 44.1% of those in the medical-therapy group. Serious adverse events related to surgical implantation or the neurostimulation device occurred in 17.7% of patients. An expert panel confirmed that medical therapy was consistent with practice guidelines for 96.8% of the patients in the neurostimulation group and for 94.5% of those in the medical-therapy group. CONCLUSIONS Subthalamic stimulation was superior to medical therapy in patients with Parkinson's disease and early motor complications. (Funded by the German Ministry of Research and others; EARLYSTIM ClinicalTrials.gov number, NCT00354133.).

The Holy Bible, according to the authorized version (A.D. 1611), with an explanatory and critical commentary and a revision of the translation, by bishops and other clergy of the Anglican church.

"Works ... referred to": New Testament, vol. I, p. lxvi-lxvii: "The principal works consulted": vol. IV, p. 493-494.

Manuel du charron et du carrossier ou L'art de fabriquer toutes sortes de voitures... avec un vocabulaire explicatif des termes techniques /

Las h. de lám. "Mm Thorel sculp."

Conocimiento de Jesucristo considerado en sus misterios y en las diferentes qualidades ó respectos que tiene para con Dios, su padre, con este mundo visible, con los hombres en sus diversos estados y con los bienaventurados en el cielo ... : van añadidas algunas meditaciones sobre los votos del Bautismo ... al fin de la obra /

Contiene: T. I (XXXII, 342 p.) -- T. II (IV, 436 p.) -- T. III (II, 429 p.) -- T. IV (IV, 494 p.)

A calendar to the feet of fines for London & Middlesex ...

I. Richard I to Richard III.--II. 1 Henry VII to Michaelmas, 11 and 12 Elizabeth.

Iron catalysed assembly of an asymmetric mixed-ligand triple helicate

The 2-pyridinecarbaldehyde isonicotinoyl hydrazone (HPCIH) family of ligands are typically tridentate N,N,O chelators that exhibit very high in vitro activity in mobilizing intracellular Fe and are promising candidates for the treatment of Fe overload diseases. Complexation of ferrous perchlorate with HPCIH in MeCN solution gives the expected six-coordinate complex Fe-II(PCIH)(2). However, complexation of Fe-II with 2-pyridinecarbaldehyde picolinoyl hydrazone (HPCPH, an isomer of HPCIH) under the same conditions leads to spontaneous assembly of an unprecedented asymmetric, mixed-ligand dinuclear triple helical complex Fe-2(II)(PCPH)(2)(PPH), where PPH2- is the dianion of bis(picolinoyl) hydrazine. The X-ray crystal structure of this complex shows that each ligand binds simultaneously to both metal centres in a bidentate fashion. The dinuclear complex exhibits two well separated and totally reversible Fe-III/II redox couples as shown by cyclic voltammetry in MeCN solution.

Direct electrochemistry of enzymes from the cytochrome P4502C family

The human cytochromes P450 are responsible for the clearance of similar to 90% of xenobiotics yet comparatively little is known about their electrochemistry. Here we report the first direct electrochemistry of P450s from the 2C subfamily; one of the major groups of enzymes from this family. Specifically, the proteins that we have examined are recombinant human P450s 2C9, 2C 18 and 2C 19 and reversible Fe-III/II couples are seen in the absence of dioxygen. Even in the presence of trace amounts of dioxygen, a pronounced cathodic response is seen which is assigned to catalytic reduction of the bound dioxygen ligand by the ferrous P450. (c) 2005 Elsevier B.V. All rights reserved.

Complexes of cytotoxic chelators from the dipyridyl ketone isonicotinoyl hydrazone (HPKIH) analogues

In an effort to better understand the antiproliferative effects of the tridentate hydrazone chelators di-2-pyridyl ketone isonicotinoyl hydrazone (HPKIH) and di-2-pyridyl ketone benzoyl hydrazone (HPKBH), we report the coordination chemistry of these ligands with the divalent metal ions, Mn, Co, Ni, Cu, and Zn. These complexes are compared with their Fe-II analogues which were reported previously. The crystal structures of Co(PKIH)(2), Ni(PKIH)(2), Cu(PKIH)(2), Mn(PKBH)(2), Ni(PKBH)(2), Cu(PKBH)(2), and Zn(PKBH)(2) are reported where similar bis-tridenate coordination modes of the ligands are defined. In pure DMF, all complexes except the Zn-II compounds exhibit metal-centered M-III/II (Mn, Fe, Co, Ni) or M-II/I (Cu) redox processes. All complexes show ligand-centered reductions at low potential. Electrochemistry in a mixed water/DMF solvent only elicited metal-centered responses from the Co and Fe complexes. Remarkably, all complexes show antiproliferative activity against the SK-N-MC neuroepithelioma cell line similar to (HPKIH) or significantly greater than that of the (HPKBH) ligand which suggests a mechanism that does not only involve the redox activity of these complexes. In fact, we suggest that the complexes act as lipophilic transport shuttles that allow entrance to the cell and enable the delivery of both the ligand and metal which act in concert to inhibit proliferation.

Transition metal complexes as mediator-titrants in protein redox potentiometry

A selection of nine macrocyclic Fe-III/II and Co-III/II transition metal complexes has been chosen to serve as a universal set of mediator-titrants in redox potentiometry of protein samples. The potential range spanned by these mediators is approximately from +300 to -700 mV vs the normal hydrogen electrode, which covers the range of most protein redox potentials accessible in aqueous solution. The complexes employed exhibit stability in both their oxidized and their reduced forms as well as pH-independent redox potentials within the range 6 < pH < 9. The mediators were also chosen on the basis of their very weak visible absorption maxima in both oxidation states, which will enable (for the first time) optical redox potentiometric titrations of proteins with relatively low extinction coefficients. This has previously been impractical with organic mediators, such as indoles, viologens and quinones, whose optical spectra interfere strongly with those of the protein.

Cobalt complexes of tripodal hexadentate ligands: Electrochemically driven rearrangements

The Co-III complexes of the hexadentate tripodal ligands HOsen (3-(2'-aminoethylamino)-2,2-bis((2 ''-aminoethylamino) methyl) propan-1-ol) and HOten (3-(2'-aminoethylthia)-2,2-bis((2 ''-aminoethylthia) methyl) propan-1-ol) have been synthesized and fully characterized. The crystal structures of [Co(HOsen)]Cl-3 center dot H2O and [Co(HOten)](ClO4)Cl-2 are reported and in both cases the ligands coordinate as tripodal hexadentate N-6 and N3S3 donors, respectively. Cyclic voltammetry of the N3S3 coordinated complex [Co(HOten)](3+) is complicated and electrode dependent. On a Pt working electrode an irreversible Co-III/II couple ( formal potential - 157 mV versus Ag-AgCl) is seen, which is indicative of dissociation of the divalent complex formed at the electrode. The free HOten released by the dissociation of [Co(HOten)](2+) can be recaptured by Hg as shown by cyclic voltammetry experiments on a static Hg drop electrode ( or in the presence of Hg2+ ions), which leads to the formation of an electroactive Hg-II complex of the N3S3 ligand (formal potential + 60 mV versus Ag-AgCl). This behaviour is in contrast to the facile and totally reversible voltammetry of the hexaamine complex [Co(HOsen)](3+) ( formal potential (Co-III/II) - 519 mV versus Ag-AgCl), which is uncomplicated by any coupled chemical reactions. Akinetic and thermodynamic analysis of the [Co(HOten)](2+)/[Hg(HOten)](2+) system is presented on the basis of digital simulation of the experimental voltammetric data.

Rotação e processos de acreção e coalescência em sistemas planetários e sistemas binários

The discovery of giant stars in the spectral regions G and K, showing moderate to rapid rotation and single behavior, namely with constant radial velocity, represents one important topic of study in Stellar Astrophysics. Indeed, such anomalous rotation clearly violates the theoretical predictions on the evolution of stellar rotation, since in evolved evolutionary stages is expected that the single stars essentially have low rotation due to the evolutionary expansion. This property is well-established from the observational point of view, with different studies showing that for single giant stars of spectral types G and K values of the rotation are typically smaller than 5kms−1 . This Thesis seeks an effective contribution to solving the paradigm described above, aiming to search for single stars of spectral types G and K with anomalous rotation, tipically rotation of moderate to rapid, in other luminosity classes. In this context, we analyzed a large stellar sample consisting of 2010 apparently single stars of luminosity classes IV, III, II and Ib with spectral types G and K, with rotational velocity v sin i and radial velocity measurements obtained from observations made by CORAVEL spectrometers. As a first result of impact we discovered the presence of anomalous rotators also among subgiants, bright giants and supergiants stars, namelly stars of luminosity classes IV, II and Ib, in contrast to previous studies, that reported anomalous rotators only in the luminosity class III classic giants. Such a finding of great significance because it allows us to analyze the presence of anomalous rotation at different intervals of mass, since the luminosity classes considered here cover a mass range between 0.80 and 20MJ, approximately. In the present survey we discovered 1 subgiant, 9 giants, 2 bright giants and 5 Ib supergiants, in spectral regions G and K, with values of v sin i ≥ 10kms−1 and single behavior. This amount of 17 stars corresponds to a frequency of 0.8% of G and K single evolved stars with anomalous rotation in the mentioned classes of luminosities, listed at the Bright Star Catalog, which is complete to visual magnitude 6.3. Given these new findings, based on a stellar sample complete in visual magnitude, as that of the Bright Star Catalog, we conducted a comparative statistical analysis using the Kolmogorov- Smirnov test, from where we conclude that the distributions of rotational velocity, v sin i, for single evolved stars with anomalous rotation in luminosity classes III and II, are similar to the distributions of v sin i for spectroscopic binary systems with evolved components with the same spectral type and luminosity class. This vii result indicates that the process of coalescence between stars of a binary system might be a possible mechanism to explain the observed abnormal rotation in the referred abnormal rotators, at least among the giants and bright giants, where the rotation in excess would be associated with the transfer of angular momentum for the star resulting from the merger. Another important result of this Thesis concerns the behavior of the infrared emission in most of the stars with anomalous rotation here studied, where 14 stars of the sample tend to have an excess in IR compared with single stars with low rotation, within of their luminosity class. This property represents an additional link in the search for the physical mechanisms responsible for the abnormal observed rotation, since recent theoretical studies show that the accretion of objects of sub-stellar mass, such as brown dwarfs and giant planets, by the hosting star, can significantly raise its rotation, producing also a circumstellar dust disk. This last result seems to point in that direction, since it is not expected that dust disks occurring during the stage of star formation can survive until the stages of subgiants, giants and supergiants Ib. In summary, in this Thesis, besides the discovery of single G and K evolved stars of luminosity classes IV, II and Ib with anomalously high rotation compared to what is predicted by stellar evolution theory, we also present the frequency of these abnormal rotators in a stellar sample complete to visual magnitude 6.3. We also present solid evidence that coalescence processes in stellar binary systems and processes of accretion of brown dwarfs star or giant planets, by the hosting stars, can act as mechanisms responsible for the puzzling phenomenon of anomalous rotation in single evolved stars.

Busca por excesso no infravermelho médio em estrelas evoluídas com fotometria WISE e 2MASS

Debris discs are commonly detected orbiting main-sequence stars, but little is known regarding their fate as stars evolve along subgiant and giant stages. Jones (2008) has found strong evidence on the presence of mid-IR excess in G and K stars of luminosity class III, using photometric data from the Two-Micron All-Sky Survey (2MASS) and GLIMPSE catalogues. While the origin of these excesses remains uncertain, it is plausible that they arise from debris discs around these stars. The present study brings an unprecedent survey in the search for mid-IR excess among single and binary F, G and K-type evolved stars of luminosity classes IV, III, II and Ib. For this study, we use WISE and 2MASS photometric data for a sample of 3000 evolved stars, complete up to visual magnitude of 6.5. As major results, we found that the frequency of evolved stars showing mid-IR WISE excess increases from the luminosity classes IV and III to luminosity classes II and Ib. In addition, there is no clear difference between the presence of IR excess in binary and single stars for all the analyzed luminosity classes.

Busca por excesso no infravermelho médio em estrelas evoluídas com fotometria WISE e 2MASS

Debris discs are commonly detected orbiting main-sequence stars, but little is known regarding their fate as stars evolve along subgiant and giant stages. Jones (2008) has found strong evidence on the presence of mid-IR excess in G and K stars of luminosity class III, using photometric data from the Two-Micron All-Sky Survey (2MASS) and GLIMPSE catalogues. While the origin of these excesses remains uncertain, it is plausible that they arise from debris discs around these stars. The present study brings an unprecedent survey in the search for mid-IR excess among single and binary F, G and K-type evolved stars of luminosity classes IV, III, II and Ib. For this study, we use WISE and 2MASS photometric data for a sample of 3000 evolved stars, complete up to visual magnitude of 6.5. As major results, we found that the frequency of evolved stars showing mid-IR WISE excess increases from the luminosity classes IV and III to luminosity classes II and Ib. In addition, there is no clear difference between the presence of IR excess in binary and single stars for all the analyzed luminosity classes.

Thermal decomposition of hydrotalcite with hexacyanoferrite(II) and hexacyanoferrate(III) anions in the interlayer : a controlled rate thermal analysis study

The mechanism for the decomposition of hydrotalcite remains unsolved. Controlled rate thermal analysis enables this decomposition pathway to be explored. The thermal decomposition of hydrotalcites with hexacyanoferrite(II) and hexacyanoferrate(III) in the interlayer has been studied using controlled rate thermal analysis technology. X-ray diffraction shows the hydrotalcites studied have a d(003) spacing of 11.1 and 10.9 Å which compares with a d-spacing of 7.9 and 7.98 Å for the hydrotalcite with carbonate or sulphate in the interlayer. Calculations based upon CRTA measurements show that 7 moles of water is lost, proving the formula of hexacyanoferrite(II) intercalated hydrotalcite is Mg6Al2(OH)16[Fe(CN)6]0.5 .7 H2O and for the hexacyanoferrate(III) intercalated hydrotalcite is Mg6Al2(OH)16[Fe(CN)6]0.66 * 9 H2O. Dehydroxylation combined with CN unit loss occurs in three steps between a) 310 and 367°C b) 367 and 390°C and c) between 390 and 428°C for both the hexacyanoferrite(II) and hexacyanoferrate(III) intercalated hydrotalcite.