Search results for "FORCE"
showing 10 items of 3423 documents
Nucleation phenomena in polymeric systems
1995
Materials formed from long flexible macromolecules differ from their small-molecule analogs, because corresponding collective length scales are distinctly larger and many dynamical phenomena are very much slower; in addition, the variation of chain length N yields a control parameter that leaves intermolecular forces invariant, but allows a stringent test of theories. These concepts are exemplified in a discussion of nucleation barriers for symmetrical polymer (A, B)-mixtures (chain lengths NA = NB = N) near the critical temperature Tc, and for symmetrical block copolymers near the (fluctuation-induced) first order transition between the disordered melt and the lamellar mesophase. While in …
Structural and dynamical characterization of melt PEO–salt mixtures
2002
Abstract Salt doped poly ethylene oxide (PEO) mixtures were investigated by means of both small angle neutron scattering and QENS techniques aiming to characterize morphological and dynamical features in the melt state. These experimental evidences provide support to the proposed heterogeneous scenario for polymer electrolytes. In particular, the existence of PEO–cation complexes is proposed to play a major role in intramolecular cooperation and intermolecular transient crosslinks, which affects the mixture properties.
Synthesis of Pyrrolidin-2-ones and of Staurosporine Aglycon (K-252c) by Intermolecular Michael Reaction
1999
Indolo[2,3-a]pyrrolo[3,4-c]carbazoles were isolated from nature, e.g., from low plants, especially fungi, as structurally rare natural substances. Responsible for naming and also the most important representative of this type is staurosporine (1), isolated from Streptomyces staurosporeus, and its aglycon (2), also known as staurosporinone or K-252c. 3,4-Disubstituted pyrrolidin-2-ones, a group of compounds with many interesting biological properties are related to staurosporinone. The most important property is the inhibition of protein kinase C (PKC), so that this antiproliferative agent can interfere with the cell cycle. The synthetic strategy, developed by us, allows the synthesis of pyr…
CFD Assisted Steady-State Modelling of Restrictive Counterbalance Valves
2020
The counterbalance valve is an important component in many hydraulic applications and its behaviour hugely impacts system stability and performance. Despite that, CBVs are rarely modelled accurately due to the effort required to obtain basic model parameters and the complexity involved in identifying expressions for flow forces and friction. This paper presents a CFD assisted approach to steady-state modelling of CBVs. It is applied to a 3-port restrictive commercially available counterbalance valve. The model obtained is based on detailed measurements of the valve geometry, a single data set and CFD modelling and includes flow forces and friction. The CFD assisted model is compared to expe…
Synthesis and Structural Characterization of Substituted 2-Phenacylbenzoxazoles
2013
1 H and 13C NMR spectra of eleven 2-phenacylbenzoxazoles (ketimine form) show that their CDCl3-solutions contains also (Z)-2-(benzo[d]oxazol-2-yl)-1-phenylethenols (enolimine form). Intramolecular hydrogen bonding in the latter tautomer was found to be significantly weaker than that one in respective (Z)-2-(2-hydroxy-2-phenylvinyl)pyridines. Integrals of the 1 H NMR signals were used to evaluate the molar ratio of the tautomers. Strong electron-donating substituents were found to stabilize the ketimine tautomer. pKT (negative logarithm of the equilibrium constant, KT = [ketimine]/[enolimine]) was found to be linearly dependent on the Hammett substituent constant σ. The results of the MP2 ab…
Beyond Pseudo‐natural Products: Sequential Ugi/Pictet‐Spengler Reactions Leading to Steroidal Pyrazinoisoquinolines That Trigger Caspase‐Independent …
2021
In this work, we describe how stereochemically complex polycyclic compounds can be generated by applying a synthetic sequence comprising an intramolecular Ugi reaction followed by a Pictet-Spengler cyclization on steroid-derived scaffolds. The resulting compounds, which combine a fragment derived from a natural product and a scaffold not found in nature. are both structurally distinct and globally similar to natural products at the same time, and interrogate an alternative region of the chemical space. One of the new compounds showed significant antiproliferative activity on HepG2 cells through a caspase-independent cell-death mechanism, an appealing feature when new antitumor compounds are…
Molecular materials with conducting and magnetic properties based on ET and [ M(tdas)2]x-dithiolenes
2004
Two hybrid molecular materials showing a combination of magnetic and conducting properties, the charge-transfer (ET) 2 [Fe(tdas) 2 ] (1) and (ET)Ni(tdas) 2 (2), (ET=bis(ethylenedithio) tetrathiafulvalene; M=Fe, Ni; tdas=l,2,5-thiadiazole-3,4-dithiolate) salts, are characterized by vibrational (IR and Raman) and UV-VIS-NIR spectroscopies. These studies have proved to be effective and diagnostic tools in identifying the oxidation state (partial or integer) and the packing pattern (dimers or segregated stacks) of the ET donor only, since no v(C=C) group vibration sensitive to the charge of M(tdas) 2 complexes has been observed. This is ascribed to the extensive electron-delocalization inside t…
Oligo(2,5-thienyleneethynylene)s with Terminal Donor-Acceptor Substitution
2006
Five oligo(2,5-thienyleneethynylene) series (OTE, n = 1–5), namely the push-pull substituted compounds 1b-5b and 1c-5c, the purely donor substituted compounds 1a-5a and two precursor series with protected and deprotected ethynyl end-groups, respectively, were obtained by a convergent synthetic strategy. The extension of the conjugated chromophores in the donor-acceptor OTE (DAOTE) series is superimposed by an intramolecular charge transfer (ICT), which decreases with an increasing number, n, of repeat units. The overall effect is studied by the convergence of the UV/Vis absorption maxima λmax (n) → λ∞ for n → ∞.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
Nucleophilic attack within Ge, Sn and Pb complexes containing Me2N(CH2)(3) - as a potential intramolecular donor ligand
1998
Abstract Thirteen tin compounds LxPhySnClz and LPh2SnPhX (x=1–4, y=0–3, z=0–2, XPh, F, Cl, Br, I, OPh), six germanium compounds LxPhyGeClz and four lead compounds LPh2PbPhX (XPh, Cl, Br, I) containing the potential intramolecular donor LMe2N(CH2)3—have been synthesized by Grignard reactions, redistribution, halogenation, exchange of halide and phenylation. Evidence for 1,5-chelation in which the donor Me2N intramolecularly attacks the Lewis-acidic atoms Ge, Sn or Pb is provided by six crystal structure determinations: Me2N(CH2)3SnPh2Cl, 5; Me2N(CH2)3SnPh2Br, 5a; Me2N(CH2)3SnPh2I, 5b; Me2N(CH2)3SnPh2OPh, 5d; Me2N(CH2)3SnPh3·HCl·H2O. 1a; Me2N(CH2)3PbPh2I, 17b), and by solution 13C, 119Sn a…
A heteropentanuclear oxalato-bridged [ReIV 4GdIII] complex: synthesis, crystal structure and magnetic properties
2012
The compound (NBu 4) 5[Gd III{Re IVBr 4(μ-ox)} 4(H 2O)]·H 2O (1), with intramolecular antiferromagnetic coupling, is the first Re(iv) system incorporating a 4f ion. © 2012 The Royal Society of Chemistry.