Search results for "polymerization"
showing 10 items of 1689 documents
Integrated experimental and computational spectroscopy study on the protonation of the α-nitronyl nitroxide radical unit
2011
The stability of the α-nitronyl nitroxide radical unit under acidic conditions is investigated by an integrated experimental UV/Vis spectroscopy and TDDFT study. In the field of molecular magnetism, α-nitronyl nitroxide radicals are important as purely organic spin carriers due to their synthetic versatility. Here, the existence of an intermediate of the protonated α-nitronyl nitroxide radical unit is demonstrated for the first time and a proposed disproportionation reaction is confirmed.
Single-molecule magnetic behavior in a neutral terbium(III) complex of a picolinate-based nitronyl nitroxide free radical
2011
The terdentate anionic picolinate-based nitronyl nitroxide (picNN) free radical forms neutral and robust homoleptic complexes with rare earth-metal ions. The nonacoordinated Tb3+ complex Tb(picNN)3• 6H2O is a single-molecule magnet with an activation energy barrier Δ = 22.8 ± 0.5 K and preexponential factor τ0 = (5.5 ± 1.1) × 10-9 s. It shows magnetic hysteresis below 1 K. © 2011 American Chemical Society.
The Tempered Polymerization of Human Neuroserpin
2012
Neuroserpin, a member of the serpin protein superfamily, is an inhibitor of proteolytic activity that is involved in pathologies such as ischemia, Alzheimer's disease, and Familial Encephalopathy with Neuroserpin Inclusion Bodies (FENIB). The latter belongs to a class of conformational diseases, known as serpinopathies, which are related to the aberrant polymerization of serpin mutants. Neuroserpin is known to polymerize, even in its wild type form, under thermal stress. Here, we study the mechanism of neuroserpin polymerization over a wide range of temperatures by different techniques. Our experiments show how the onset of polymerization is dependent on the formation of an intermediate mon…
On the molecular structure of human neuroserpin polymers
2012
The polymerization of serpins is at the root of a large class of diseases; the molecular structure of serpin polymers has been recently debated. In this work, we study the polymerization kinetics of human neuroserpin by Fourier Transform Infra Red spectroscopy and by time-lapse Size Exclusion Chromatography. First, we show that two distinct neuroserpin polymers, formed at 45 and 85°C, display the same isosbestic points in the Amide I' band, and therefore share common secondary structure features. We also find a concentration independent polymerization rate at 45°C suggesting that the polymerization rate-limiting step is the formation of an activated monomeric species. The polymer structures…
Pyrophosphate-mediated magnetic interactions in Cu(II) coordination complexes.
2010
The reaction in water of Cu(NO(3))(2)·2.5H(2)O with 2,2'-bipyridine (bipy), 1,10-phenanthroline (phen), or 1,10-phenanthroline-5-amine (phenam), and sodium pyrophosphate (Na(4)P(2)O(7)), at various pHs, afforded three new copper(II)-pyrophosphate complexes, namely, {[Cu(bipy)(cis-H(2)P(2)O(7))](2)}·3H(2)O (1a), {[Cu(phen)(H(2)O)](4)(HP(2)O(7))(2)}(ClO(4))(2)·4H(2)O (2), and {[Cu(2)(phenam)(2)(P(2)O(7))](2)·25H(2)O}(n) (3). A solvent free crystalline phase of 1a was also isolated with formula {[Cu(bipy)(trans-H(2)P(2)O(7))](2)} (1b), which can be regarded as a pseudo-polymorph of 1a. Single crystal X-ray analyses revealed these compounds to have uncommon molecular architectures, with 3 being…
Development of Bimetallic Titanocene−Ruthenium−Arene Complexes As Anticancer Agents: Relationships between Structural and Biological Properties
2010
A series of bimetallic titanium-ruthenium complexes of general formula [(η(5)-C(5)H(5))(μ-η(5):κ(1)-C(5)H(4)(CR(2))(n)PR'R'')TiCl(2)](η(6)-p-cymene)RuCl(2) (n = 0, 1, 2 or 4; R = H or Me; R' = H, Ph, or Cy; R'' = Ph or Cy) have been synthesized, including two novel compounds as well as two cationic derivatives of formula [(η(5)-C(5)H(5))(μ-η(5):κ(1)-C(5)H(4)(CH(2))(n)PPh(2))TiCl(2)] [(η(6)-p-cymene)RuCl](BF(4)) (n = 0 or 2). The solid state structure of two of these compounds was also established by X-ray crystallography. The complexes showed a cytotoxic effect on human ovarian cancer cells and were markedly more active than their Ti or Ru monometallic analogues titanocene dichloride and RA…
Synthesis, characterization and properties of functional star and dendritic block copolymers of ethylene oxide and glycidol with oligoglycidol branch…
2009
Abstract Well-defined, four-arm star block copolymers of ethylene oxide and glycidol were prepared via controlled anionic polymerization using protected glycidol. The length of the poly(ethylene oxide) block was varied from DP = 10 to 50, while the length of the short polyglycidol block remained nearly constant, at DP = 4–6. Star block copolymers with hydroxyl groups at the ends of the arms after conversion to the corresponding alkoxides were used as multifunctional macroinitiators for the sequential polymerization of ethylene oxide and protected glycidol. After deprotection, the branched block copolymers of ethylene oxide and glycidol had narrow molar mass distributions and multiple hydrox…
ALTMET Polymerization of Amino Acid-Based Monomers Targeting Controlled Drug Release
2016
Giving the imminent necessity of a new generation of biodegradable and biocompatible polymers prepared from feedstock, the synthesis of a potentially biodegradable amino acid-based copolymer by the alternating diene metathesis (ALTMET) strategy is herein presented. The reaction was tailored to minimize isomerization and deactivation of ruthenium catalysts by intramolecular coordination with the amide carbonyl group of the amino-acid-based monomer. Alternated l-lysine–phosphoester copolymers with molar masses higher than 18 000 g/mol were obtained using Hoveyda–Grubbs second-generation and Umicore M2 catalysts. The copolymer was further used to prepare nanoparticles loaded with rifampicin (u…
Hyperbranched Poly(ethylene glycol) Copolymers: Absolute Values of the Molar Mass, Properties in Dilute Solution, and Hydrodynamic Homology
2015
Hyperbranched poly(ethylene glycol) copolymers were synthesized by random anionic ring-opening multibranching copolymerization of ethylene oxide with glycidol as a branching agent, leading to poly(ethylene glycol) structure with glycerol branching points. Extending the available range of molar masses by novel synthesis strategies, a limited extent of control over the degree of polymerization was achieved by variation of the solvent in this copolymerization. Generally, absolute molar mass characterization of hyperbranched polymers still represents an unresolved challenge. A series of the hyperbranched poly(ethylene glycol)-co-(glycerol) copolymers (hbPEGs) of a wide range of molar masses (14…
Effect of adhesive layers on microshear bond strength of nanocomposite resin to dentin
2016
BACKGROUND Bond strength of adhesive layer can absorb unwanted stresses of polymerization shrinkage in composite resin restorations; increased microshear bond strength can prevent failure of restoration materials, the purpose of this study was to evaluate the effect of adhesive layers on microshear bond strength of nanocomposite resin to dentin. MATERIAL AND METHODS Two different types of adhesive systems: universal adhesive (ExciTE) and newly developed adhesive (Nano-Bond), and one type of light-cured resin restorative material (Nanocomposite resin) were used in this study. The occlusal surfaces of extracted human molar teeth were ground perpendicular to the long axis of each tooth to expo…