Search results for "steric"

Ligand Design for Heterobimetallic Single-Chain Magnets: Synthesis, Crystal Structures, and Magnetic Properties of MIICuII (M=Mn, Co) Chains with Ste…

2006

Two new series of neutral ox-amato-bridged heterobimetallic chains of general formula [MCu(L x ) 2 ]- m DMSO (m=0-4) (L 1 =N-2-methyl-phenyloxamate, M=Mn (1a) and Co (1 b); L2 = N-2,6-dimethylphenyloxamate, M=Mn (2a) and Co (2b); L 3 = N-2,4,6-trimethylphenyloxamate, M= Mn (3a) and Co (3b)) have been prepared by reaction between the corresponding anionic oxamatocopper(II) complexes [Cu(L x ) 2 ] 2- with Mn 2+ or Co 2+ cations in DMSO. The crystal structures of [CoCu(L 2 ) 2 (H 2 O) 2 ] (2b') and [CoCu(L 3 ) 2 (H 2 O) 2 ]·4H 2 O (3b') have been solved by single-crystal X-ray diffraction methods. Compounds 2b' and 3b' adopt zigzag and linear chain structures, respectively. The intrachain Cu··…

1981

The anionic polymerization of tert-butyl methacrylate (TBMA) in tetrahydrofuran, using Na+ and Cs+ as counterions proceeds without side reactions even at room temperature. The resulting molecular weight distributions are nearly monodisperse (Mw/Mn ⩽ 1,01). The rate constants for the propagation of ion pairs were measured in the range from + 15 to −100°C. The Arrhenius plots are linear, but different for the two counterions, resulting in the following numerical values for the frequency exponent A and the activation energy Ea: A = 8,5 and Ea = 7,2 kcal/mol = 30 kJ/mol for Na+; A = 9,5 and Ea = 5,6 kcal/mol = 23 kJ/mol for Cs+. The difference between the counterions, which is in contrast to th…

Nested allosteric interactions in extracellular hemoglobin of the leech Macrobdella decora

2003

Hemoglobin from the leech Macrobdella decora belongs to the class of giant extracellular hexagonal bilayer globin structures found in annelid and vestimentiferan worms. These complexes consist of 144 heme-bearing subunits, exhibit a characteristic quaternary structure (2 × (6 × (3 × 4))), and contain tetramers as basic substructures that express cooperative oxygen binding and thus provide a structural basis for a hierarchy in allosteric interactions. A thorough analysis of the isolated tetramer indicates that it functions as a trimer of cooperatively interacting subunits and a non-cooperative monomer rather than as four interacting subunits. A thermodynamic analysis of the whole molecule fa…

Sterically crowded triazenides as novel ancillary ligands in copper chemistry

2011

Abstract We have synthesized copper salts MN3RR′ derived from the biphenyl- or m-terphenyl-substituted triazenes Tph2N3H (1a) and Dmp(Tph)N3H (1b) (Dmp = 2,6-Mes2C6H3 with Mes = 2,4,6-Me3C6H2; Tph = 2-TripC6H4 with Trip = 2,4,6-i-Pr3C6H2). The homoleptic copper triazenide [CuN3Tph2] (2a) was obtained in high yield from the metallation of 1a with mesityl copper in n-heptane, while the complex [CuN3(Dmp)Tph] (2b) was generated by the same method in situ only. Reaction of 2a with triphenylphosphane gave the 2:1 adduct [CuN3Tph2(PPh3)2] (3a), regardless of the used complex/donor ratio, while reaction of 2a or 2b with a stochiometric amount of t-butylisonitrile afforded the 1:1 adducts [Tph2N3Cu…

Anti-inflammatory lipoxin A4 is an endogenous allosteric enhancer of CB1 cannabinoid receptor.

2012

Allosteric modulation of G-protein–coupled receptors represents a key goal of current pharmacology. In particular, endogenous allosteric modulators might represent important targets of interventions aimed at maximizing therapeutic efficacy and reducing side effects of drugs. Here we show that the anti-inflammatory lipid lipoxin A 4 is an endogenous allosteric enhancer of the CB 1 cannabinoid receptor. Lipoxin A 4 was detected in brain tissues, did not compete for the orthosteric binding site of the CB 1 receptor (vs. 3 H-SR141716A), and did not alter endocannabinoid metabolism (as opposed to URB597 and MAFP), but it enhanced affinity of anandamide at the CB1 receptor, thereby potentiating …

Selectivity of pharmacological tools: implications for use in cell physiology. A Review in the Theme: Cell Signaling: Proteins, Pathways and Mechanis…

2014

Pharmacological inhibitors are frequently used to identify the receptors, receptor subtypes, and associated signaling pathways involved in physiological cell responses. Based on the effects of such inhibitors conclusions are drawn about the involvement of their assumed target or lack thereof. While such inhibitors can be useful tools for a better physiological understanding, their uncritical use can lead to incorrect conclusions. This article reviews the concept of inhibitor selectivity and its implication for cell physiology. Specifically, we discuss the implications of using inhibitor vs. activator approaches, issues of direct vs. indirect pathway modulation, implications of inverse agoni…

Design of enzyme-mediated controlled release systems based on silica mesoporous supports capped with ester-glycol groups

2012

[EN] An ethylene glycol-capped hybrid material for the controlled release of molecules in the presence of esterase enzyme has been prepared. The final organic-inorganic hybrid solid S1 was synthesized by a two-step procedure. In the first step, the pores of an inorganic MCM-41 support (in the form of nanoparticles) were loaded with [Ru(bipy) 3]Cl 2 complex, and then, in the second step, the pore outlets were functionalized with ester glycol moieties that acted as molecular caps. In the absence of an enzyme, release of the complex from aqueous suspensions of S1 at pH 8.0 is inhibited due to the steric hindrance imposed by the bulky ester glycol moieties. Upon addition of esterase enzyme, del…

Dinuclear chloroneodymium quinolinylcarboxylates: The molecular structures affected by water and the catalytic behavior toward isoprene polymerization

2016

Abstract A series of dinuclear chloroneodymium quinolinylcarboxylate compounds was synthesized and characterized. The nature and importance of metal-organic aggregations have been considered as an important factor regarding the molecular structure and catalytic performance. The neodymium center in all the title compounds exhibits the coordination numbers of 8. Cage aggregation was observed in the solid state, and the cyclic arrangement was achieved when water molecules were incorporated into the structure. Upon the activation with Al(i-Bu)3, all the title neodymium compounds form the efficient catalysts for isoprene polymerization. The catalytic activities are not strongly affected by the m…

Synthesis, characterization and X-ray crystal structures of cyclam derivatives. 7. Hydrogen-bond induced allosteric effects and protonation cooperati…

2005

The unprecedented cooperative protonation properties displayed by a barrel-shaped macrotricyclic tetraamine incorporating two 14-membered bisamide rings maintained in a face-to-face arrangement is rationalized in terms of allosteric effects upon binding of the first and third protons.

Allosteric modulation of nicotinic acetylcholine receptors as a treatment strategy for Alzheimer's disease

2000

The basic symptoms of Alzheimer's dementia, i.e., a loss in cognitive function, are due to impaired nicotinic cholinergic neurotransmission. To compensate for this impairment by drug treatment, blockers of the acetylcholine-degrading enzyme acetylcholinesterase are applied, even though this approach obviously is prone to many side-effects, including those of muscarinic nature. We have recently described a novel class of nicotinic acetylcholine receptor ligands which, similar to the action of benzodiazepines on GABA(A) receptors, allosterically potentiate submaximal nicotinic responses. The sensitizing effect is a consequence of facilitated channel opening in the presence of allosterically p…