Amphiphile Verbindungen der 14. Gruppe - Synthese, Eigenschaften und Anwendungen von Organosilanolen

Im Rahmen dieser Dissertation wurde an der Darstellung stabiler, amphiphiler Silantriole gearbeitet. Es ist gelungen eine kontinuierliche Reihe sukzessive um CH2-Einheiten verlängerter Silantriole des Typs H3C(CH2)nC(CH3)2Si(OH)3 (n = 1-5) durch eine vierstufige Synthesesequenz ausgehend von n-Alkylbromiden herzustellen und zum Teil röntgenographisch zu untersuchen. Ihre oberflächenaktiven Eigenschaften in wässrigen Lösungen konnten erstmals mittels Oberflächenspannungsmessungen belegt werden. Durch gezielte Kondensationsreaktionen mit Trifluoressigsäure wurden ausgehend von den oben beschriebenen Silantriolen selektiv die entsprechenden Disiloxan-Tetrole erhalten und ebenfalls zum Teil durch Röntgenstrukturanalysen charakterisiert. Als weitere Kondensationsprodukte der Silantriole konnten die ersten Octasilsesquioxane mit tertiären Kohlenstoff-Substituenten durch Umsetzungen mit n-Bu4NF selektiv und in hohen Ausbeuten erhalten und ebenfalls röntgenographisch identifiziert werden. Es wurde an der Darstellung Aryl-substituierter Silantriole RSi(OH)3 (R = Mesityl-, Xylyl- und Tetramethyl-phenyl-) gearbeitet. Diese zeichnen sich jedoch durch ihre hohe Instabilität in Lösung und im Festkörper aus und konnten zum Teil nur zusammen mit ihren primären Kondensationsprodukten erhalten werden. Darüber hinaus wurden stabile Silandiole des Typs R(t-Bu)Si(OH)2 (R = n-Butyl und n-Pentyl) sowie das (o-CF3C6H4)2Si(OH)2 in hohen Ausbeuten und selektiv synthetisiert. Die Festkörpereigenschaften des (o-CF3C6H4)2Si(OH)2 sowie seiner Vorstufe (o-CF3C6H4)2SiCl2 konnten durch Kristallstrukturanalysen genauer untersucht werden. In der Arbeit wurden die ersten Anwendungen von Silanolen als Silan-Kupplungsreagenzien bei der Oberflächenmodifizierung von Glas beschrieben. Im Gegensatz zu gängigen säureassistierten Beschichtungen zeichnen sich diese Silanol-Beschichtungen durch eine deutlich höhere Hydrophobizität aus. Dies konnte durch Kontaktwinkel- und Zeta-Potential-Messungen bestätigt werden. Durch Röntgenreflektivitäts- und Sarfus-Messungen ist die Ausbildung von Monolagen im Falle von t-BuSi(OH)3-beschichteten Oberflächen plausibel. Die Oberflächenmorphologie der Silantriol-Beschichtungen wurde mittels AFM-Messungen untersucht. Die Si(OH)3-Funktion konnte in der vorliegenden Arbeit als ein neues Pharmakophor etabliert werden. Die Silantriole CySi(OH)3, TerSi(OH)3 und CH3CH2C(CH3)2Si(OH)3 (Cy = Cyclohexyl, Ter = Terphenyl) sind in der Lage das Enzym Acetylcholinesterase reversibel zu hemmen. Dabei zeigt das CySi(OH)3 mit 45 % relativ zur Kontrolle die höchste Inhibition.

Responsabilidad del estado por la actividad médicas en Colombia

El ejercicio de la medicina en nuestro país ha cambiado en forma radical en los últimos años. La aparición de las demandas médicas ya ha llevado a ejercer una medicina defensiva, con un mayor deterioro de la relación médico paciente

Preparation and properties of gallaborane, GaBH6: structure of the gaseous molecule H2Ga(μ-H)2BH2 as determined by vibrational, electron diffraction, and ab initio studies, and structure of the crystalline solid at 110 K as determined by x-ray diffraction``

Gallaborane (GaBH6, 1), synthesized by the metathesis of LiBH4 with [H2GaCl]n at ca. 250 K, has been characterized by chemical analysis and by its IR and 1H and 11B NMR spectra. The IR spectrum of the vapor at low pressure implies the presence of only one species, viz. H2Ga(μ-H)2BH2, with a diborane-like structure conforming to C2v symmetry. The structure of this molecule has been determined by gas-phase electron diffraction (GED) measurements afforced by the results of ab initio molecular orbital calculations. Hence the principal distances (rα in Å) and angles ( α in deg) are as follows: r(Ga•••B), 2.197(3); r(Ga−Ht), 1.555(6); r(Ga−Hb), 1.800(6); r(B−Ht), 1.189(7); r(B−Hb), 1.286(7); Hb−Ga−Hb, 71.6(4); and Hb−B−Hb, 110.0(5) (t = terminal, b = bridging). Aggregation of the molecules occurs in the condensed phases. X-ray crystallographic studies of a single crystal at 110 K reveal a polymeric network with helical chains made up of alternating pseudotetrahedral GaH4 and BH4 units linked through single hydrogen bridges; the average Ga•••B distance is now 2.473(7) Å. The compound decomposes in the condensed phases at temperatures exceeding ca. 240 K with the formation of elemental Ga and H2 and B2H6. The reactions with NH3, Me3N, and Me3P are also described.

Asymmetric aziridine synthesis by aza-Darzens reaction of N-diphenylphosphinylimines with chiral enolates. Part 2: inversion of diastereoselectivity

The aza-Darzens ('ADZ') reactions of N-diphenylphosphinyl ('N-Dpp') imines with chiral enolates derived from N-bromoacetyl 2S-2,10-camphorsultam proceed in generally good yield to give N-diphenylphosphinyl aziridinoyl sultams. However, the stereoselectivity of the reaction is dependent upon the structure of the imine substituent: when the chiral enolate was reacted with arylimines substituted in the ortho-position, mixtures of cis- and trans-2'R,3'R-aziridines were obtained, often with a complete selectivity in favour of the trans-isomer. (c) 2006 Elsevier Ltd. All rights reserved.

Asymmetric aziridine synthesis by aza-Darzens reaction of N-diphenylphosphinylimines with chiral enolates. Part 1: formation of cis-aziridines

Theaza-Darzens ('ADZ') reactions off-diphenylphosphinyl (W-Dpp') imines with chiral enolates derived from oxazolidinones and camphorsultam have been Studied. Whilst oxazolidinone enolates reacted poorly in terms of aziridination, the use of the chiral enolate derived from both antipodes of N-bromoacetyl 2, 10-camphorsultam, 2R-(5) and 2S-(5), with N-diphehenylphosphinyl aryl and tert-butylimines proceeded in generally good yield to give, respectively, (2'R,3'R)- or (2'S,3'S)-cis-N-diphenylphosphinyl aziridinoyl sultams of high de. (c) 2006 Elsevier Ltd. All rights reserved.

Gender differences in early accommodation and vergence development

A remote haploscopic photorefractor was used to assess objective binocular vergence and accommodation responses in 157 full-term healthy infants aged 1-6 months while fixating a brightly coloured target moving between fixation distances at 2, 1, 0.5 and 0.33 m. Vergence and accommodation response gain matured rapidly from 'flat' neonatal responses at an intercept of approximately 2 dioptres (D) for accommodation and 2.5 metre angles(MA) for vergence, reaching adult-like values at 4 months. Vergence gain was marginally higher in females (p = 0.064), but accommodation gain (p = 0.034) was higher and accommodative intercept closer to zero (p = 0.004) in males in the first 3 months as they relaxed accommodation more appropriately for distant targets. More females showed flat accommodation responses (p = 0.029). More males behaved hypermetropically in the first two months of life, but when these hypermetropic infants were excluded from the analysis, the gender difference remained. Gender differences disappeared after three months. Data showed variable responses and infants could behave appropriately and simultaneously on both, neither or only one measure at all ages. If accommodation was appropriate (gain between 0.7 and 1.3; r(2) > 0.7) but vergence was not, males over- and under-converged equally, while the females who accommodated appropriately were more likely to overconverge (p = 0.008). The apparent earlier maturity of the male accommodative responses may be due to refractive error differences but could also reflect gender-specific male preference for blur cues while females show earlier preference for disparity, which may underpin the earlier emerging, disparity dependent, stereopsis and full vergence found in females in other studies.

An unexpected photoadduct of N-carbomethoxymethylpyrrolidine with a chiral butenolide and benzophenone: X-ray structure and synthetic utility

The regio- and stereoselective photoinduced addition of N-carbomethoxymethylpyrrolidine to 5(S)-tert-butyldimethylsiloxymethyl-furan-2(5H)-one in the presence of benzophenone yields 3(R)-[N-(diphenylhydroxymethyl)carbo methoxymethylpyrrolidin-2′-yl]-4(S)-tert-butyldimethylsiloxymethyl)-butan-4-olides (epimeric at C-2′), and we report the X-ray structure of the major adduct together with its conversion into the 1-azabicyclo[4.3.0]-nonane ring system.

When do export subsidies have a redistributional role? Reply

Our differences are three. The first arises from the belief that "... a nonzero value for the optimally chosen policy instrument implies that the instrument is efficient for redistribution" (Alston, Smith, and Vercammen, p. 543, paragraph 3). Consider the two equations: (1) o* = f(P3) and (2) = -f(3) ++r h* (a, P3) representing the solution to the problem of maximizing weighted, Marshallian surplus using, simultaneously, a per-unit border intervention, 9, and a per-unit domestic intervention, wr. In the solution, parameter ot denotes the weight applied to producer surplus; parameter p denotes the weight applied to government revenues; consumer surplus is implicitly weighted one; and the country in question is small in the sense that it is unable to affect world price by any of its domestic adjustments (see the Appendix). Details of the forms of the functions f((P) and h(ot, p) are easily derived, but what matters in the context of Alston, Smith, and Vercammen's Comment is: Redistributivep referencest hatf avorp roducers are consistent with higher values "alpha," and whereas the optimal domestic intervention, 7r*, has both "alpha and beta effects," the optimal border intervention, r*, has only a "beta effect,"-it does not have a redistributional role. Garth Holloway is reader in agricultural economics and statistics, Department of Agricultural and Food Economics, School of Agriculture, Policy, and Development, University of Reading. The author is very grateful to Xavier Irz, Bhavani Shankar, Chittur Srinivasan, Colin Thirtle, and Richard Tiffin for their comments and their wisdom; and to Mario Mazzochi, Marinos Tsigas, and Cal Turvey for their scholarship, including help in tracking down a fairly complete collection of the papers that cite Alston and Hurd. They are not responsible for any errors or omissions. Note, in equation (1), that the border intervention is positive whenever a distortion exists because 8 > 0 implies 3 - 1 + 8 > 1 and, thus, f((P) > 0 (see Appendix). Using Alston, Smith, and Vercammen's definition, the instrument is now "efficient," and therefore has a redistributive role. But now, suppose that the distortion is removed so that 3 - 1 + 8 = 1, 8 = 0, and consequently the border intervention is zero. According to Alston, Smith, and Vercammen, the instrument is now "inefficient" and has no redistributive role. The reader will note that this thought experiment has said nothing about supporting farm incomes, and so has nothing whatsoever to do with efficient redistribution. Of course, the definition is false. It follows that a domestic distortion arising from the "excess-burden argument" 3 = 1 + 8, 8 > 0 does not make an export subsidy "efficient." The export subsidy, having only a "beta effect," does not have a redistributional role. The second disagreement emerges from the comment that Holloway "... uses an idiosyncratic definition of the relevant objective function of the government (Alston, Smith, and Vercammen, p. 543, paragraph 2)." The objective function that generates equations (1) and (2) (see the Appendix) is the same as the objective function used by Gardner (1995) when he first questioned Alston, Carter, and Smith's claim that a "domestic distortion can make a border intervention efficient in transferring surplus from consumers and taxpayers to farmers." The objective function used by Gardner (1995) is the same objective function used in the contributions that precede it and thus defines the literature on the debate about borderversus- domestic intervention (Streeten; Yeh; Paarlberg 1984, 1985; Orden; Gardner 1985). The objective function in the latter literature is the same as the one implied in another literature that originates from Wallace and includes most notably Gardner (1983), but also Alston and Hurd. Amer. J. Agr. Econ. 86(2) (May 2004): 549-552 Copyright 2004 American Agricultural Economics Association This content downloaded on Tue, 15 Jan 2013 07:58:41 AM All use subject to JSTOR Terms and Conditions 550 May 2004 Amer. J. Agr. Econ. The objective function in Holloway is this same objective function-it is, of course, Marshallian surplus.1 The third disagreement concerns scholarship. The Comment does not seem to be cognizant of several important papers, especially Bhagwati and Ramaswami, and Bhagwati, both of which precede Corden (1974, 1997); but also Lipsey and Lancaster, and Moschini and Sckokai; one important aspect of Alston and Hurd; and one extremely important result in Holloway. This oversight has some unfortunate repercussions. First, it misdirects to the wrong origins of intellectual property. Second, it misleads about the appropriateness of some welfare calculations. Third, it prevents Alston, Smith, and Vercammen from linking a finding in Holloway (pp. 242-43) with an old theorem (Lipsey and Lancaster) that settles the controversy (Alston, Carter, and Smith 1993, 1995; Gardner 1995; and, presently, Alston, Smith, and Vercammen) about the efficiency of border intervention in the presence of domestic distortions.

Modelling signatures of pulsed magnetopause reconnection in cusp ion dispersion signatures seen at middle altitudes

It is shown that the open magnetosphere model can reproduce both the down-going and the up-going magnetosheath ions seen in the cusp and mantle regions by the Polar satellite at middle altitudes. ?he pass studied shows a series of discontinuities in the ion dispersion, most of which are shown to arise from pulses of magnetopause reconnection rate. A total of 9 pulses are detected in an interval estimated to be about 30 min long, giving a mean repetition period of about 3 min: they vary in length between 0.5 min and 3.5 min and are separated by periods of much slower reconnection of duration 1-3 min. One step is not as predicted for reconnection rate pulses but is explained in terms of compressive motions caused by a pulse of solar wind dynamic pressure. The reconnection site is found to be 16 +/- 3 R-E from the ionosphere along the separatrix field line, placing it at low latitudes on the dayside magnetopause.

Understanding complexities in international accounting standard setting: agenda entry and the case of IFRS for SMEs

Earlier accounting works have shown that an understanding of agenda entry is critical to better understanding the accounting standards setting process. Consider Walker and Robinson (1993; 1994) and Ryan (1998); and more generally agenda entrance as theorized in Kingdon (2011). In 2003, the IASB placed on its agenda a project to promulgate a standard for small and medium-sized entities (SMEs). This provides our focus. It seemed to be a departure from the IASB’s constitutional focus on capital market participants. Kingdon’s three-streams model of agenda entry helps to identify some of the complexities related to politics and decision making messiness that resulted in a standard setting project for simplified IFRS, misleadingly titled IFRS for SMEs. Complexities relate to the broader international regulatory context, including the boundaries of the IASB’s standard-setting jurisdiction, the role of board members in changing those boundaries, and such sensitivities over the language that the IASB could not agree on a suitably descriptive title. The paper shows similarities with earlier agenda entrance studies by Walker and Robinson (1994) and Ryan (1998). By drawing on interviewees’ recollections and other material it especially reinforces the part played by the nuanced complexities that influence what emerges as an international accounting standard.

Transit times – the link between hydrology and water quality at the catchment scale

In spite of trying to understand processes in the same spatial domain, the catchment hydrology and water quality scientific communities are relatively disconnected and so are their respective models. This is emphasized by an inadequate representation of transport processes, in both catchment-scale hydrological and water quality models. While many hydrological models at the catchment scale only account for pressure propagation and not for mass transfer, catchment scale water quality models are typically limited by overly simplistic representations of flow processes. With the objective of raising awareness for this issue and outlining potential ways forward we provide a non-technical overview of (1) the importance of hydrology-controlled transport through catchment systems as the link between hydrology and water quality; (2) the limitations of current generation catchment-scale hydrological and water quality models; (3) the concept of transit times as tools to quantify transport and (4) the benefits of transit time based formulations of solute transport for catchment-scale hydrological and water quality models. There is emerging evidence that an explicit formulation of transport processes, based on the concept of transit times has the potential to improve the understanding of the integrated system dynamics of catchments and to provide a stronger link between catchment-scale hydrological and water quality models.

Regularity of solutions on the global attractor for a semilinear damped wave equation

We consider attractors A(eta), eta epsilon [0, 1], corresponding to a singularly perturbed damped wave equation u(tt) + 2 eta A(1/2)u(t) + au(t) + Au = f (u) in H-0(1)(Omega) x L-2 (Omega), where Omega is a bounded smooth domain in R-3. For dissipative nonlinearity f epsilon C-2(R, R) satisfying vertical bar f ``(s)vertical bar <= c(1 + vertical bar s vertical bar) with some c > 0, we prove that the family of attractors {A(eta), eta >= 0} is upper semicontinuous at eta = 0 in H1+s (Omega) x H-s (Omega) for any s epsilon (0, 1). For dissipative f epsilon C-3 (R, R) satisfying lim(vertical bar s vertical bar) (->) (infinity) f ``(s)/s = 0 we prove that the attractor A(0) for the damped wave equation u(tt) + au(t) + Au = f (u) (case eta = 0) is bounded in H-4(Omega) x H-3(Omega) and thus is compact in the Holder spaces C2+mu ((Omega) over bar) x C1+mu((Omega) over bar) for every mu epsilon (0, 1/2). As a consequence of the uniform bounds we obtain that the family of attractors {A(eta), eta epsilon [0, 1]} is upper and lower semicontinuous in C2+mu ((Omega) over bar) x C1+mu ((Omega) over bar) for every mu epsilon (0, 1/2). (c) 2007 Elsevier Inc. All rights reserved.

Towards a maximal extension of Pelczynski`s decomposition method in Banach spaces

l Suppose that X, Y. A and B are Banach spaces such that X is isomorphic to Y E) A and Y is isomorphic to X circle plus B. Are X and Y necessarily isomorphic? In this generality. the answer is no, as proved by W.T. Cowers in 1996. In the present paper, we provide a very simple necessary and sufficient condition on the 10-tuples (k, l, m, n. p, q, r, s, u, v) in N with p+q+u >= 3, r+s+v >= 3, uv >= 1, (p,q)$(0,0), (r,s)not equal(0,0) and u=1 or v=1 or (p. q) = (1, 0) or (r, s) = (0, 1), which guarantees that X is isomorphic to Y whenever these Banach spaces satisfy X(u) similar to X(p)circle plus Y(q), Y(u) similar to X(r)circle plus Y(s), and A(k) circle plus B(l) similar to A(m) circle plus B(n). Namely, delta = +/- 1 or lozenge not equal 0, gcd(lozenge, delta (p + q - u)) divides p + q - u and gcd(lozenge, delta(r + s - v)) divides r + s - v, where 3 = k - I - in + n is the characteristic number of the 4-tuple (k, l, m, n) and lozenge = (p - u)(s - v) - rq is the discriminant of the 6-tuple (p, q, r, s, U, v). We conjecture that this result is in some sense a maximal extension of the classical Pelczynski`s decomposition method in Banach spaces: the case (1, 0. 1, 0, 2. 0, 0, 2. 1. 1). (C) 2009 Elsevier Inc. All rights reserved.

A NOTE ON THE COMPOSITE OF TWO IRREDUCIBLE MORPHISMS

In this note, we show that a composite of two irreducible morphisms between indecomposable modules cannot lie in R(3)\R(5).

Spectroscopic and theoretical studies of some N-methoxy-N-methyl-2-[(4 `-substituted) phenylsulfonyl]propanamides

The analysis of the IR carbonyl band of the N-methoxy-N-methyl-2-[(4`-substituted)phenyisulfonyI]propanamides Y-PhSO(2)CH(Me)C(O)N(OMe)Me (Y = OMe 1, Me 2, H 3, Cl 4, NO(2) 5), supported by HF/6-31G(d,p) calculations of 3,, indicated the existence of two gauche conformers (g(1) and g(2)), the g, conformer being the most stable and the least polar one (in gas phase and in solution). Both conformers are present in solution of the non polar solvent (CCl(4)) for 1-5 and in solution of the more polar solvents (CHCl(3)) for 1. 4, 5 and (CH(2)Cl(2)) for 5, while only the g(1) conformer is present in solution of the most polar solvent (CH(3)CN) for 1-5. The g, and g2 conformers correspond to the enantiomeric pairs of diastereomers (diast(1) and diast(2)) whose relative configurations are [C(3)(R)N(R)]/[C(3)(s)N(s)] and [C(3)(R)N(s)]/[C(3)(s)N(R)], respectively. The computed carbonyl frequencies for g(1) (diast(1)) and g(2) (diast(2)) stereoisomers of3 match well the experimental values. The NBO analysis, for 3 shows the important role of the orbital interactions in conformer stabilization and the overall balance of these interactions corroborates that the g, conformer is more stable than the 92 one. The observed abnormal solvent effect on the relative intensities of the carbonyl doublet components is attributed to the molecular crowding in the g2 conformer which hinders its solvation in comparison to the g, conformer (diast(1)). X-ray single crystal analysis performed for 3 shows the existence Of two 92, and g(1b) conformers of diastereomers (diast2, and diast(1b)) whose absolute configurations are [C(3)(R)N(s)] and [C(3)(R)N(R)], respectively. The larger population and. thus, the larger stabilization of the g(2), conformer over the gib form in the crystals may be associated with a larger energy gain deriving from dipole moment coupling in the former conformer along with a series of C-H center dot center dot center dot O electrostatic and hydrogen bond interactions, (C) 2009 Elsevier B.V. All rights reserved.