Kinetics of the self-assembly of bold alpha -cyclodextrin [2]pseudorotaxanes with polymethylene threads bearing quaternary ammonium and phosphonium end groups

1998 ◽  
Vol 76 (6) ◽  
pp. 843-850
Author(s):  
Angela P Lyon ◽  
Nicola J Banton ◽  
Donal H Macartney
Keyword(s):  
Rate Constant ◽  
Self Assembly ◽  
Elevated Temperatures ◽  
Formation Rate ◽  
Minor Effect ◽  
Prolonged Heating ◽  
End Groups ◽  
A Minor ◽  
Kinetics Of

The kinetics and mechanism of the formation and dissociation of a series of [2]pseudorotaxanes, comprised of α -cyclodextrin (α -CD) as the cyclic component and the ([Me3N(CH2)nNMe3]2+ (n = 8-12), [Me2EtN(CH2)10NEtMe2]2+, and [Me3P(CH2)10PMe3]2+) dications as the threads, were determined by means of 1H and 31P NMR in aqueous solution. The length of the polymethylene chain (n) of the thread, which has a minor effect on the rate constant for pseudorotaxane formation, is important in the kinetics of the dissociation reactions, with the longer, more hydrophobic chains resulting in slower pseudorotaxane dissociation. The replacement of one methyl substitutent by an ethyl group in each of the end groups on the [Me3N(CH2)10NMe3]2+ thread results in a 30-fold decrease in the formation rate constant. Replacements, by ethyls, of two or all of the methyl substitutents prevent the formation of the pseudorotaxane, even after prolonged heating. The pseudorotaxane containing the {Me3P(CH2)10PMe3.; α-CD}2+ thread forms only at elevated temperatures by a slippage mechanism, and the rate constant for its self-assembly at 75°C (8 x 10-5 M-1 s-1) is more than 106 smaller than the rate constant at 75°C (200 M-1 s-1) extrapolated for the corresponding {Me3N(CH2)10NMe3 . α -CD}2+complex. The enthalpies and entropies of activation for the formation and dissociation of the [2]pseudorotaxanes decrease with an increase in the size and hydrophobicity of the end groups, suggesting a reduced role of desolvation of the quaternized atoms in the threading or dethreading processes.Key words: pseudorotaxane, α -cyclodextrin, kinetics, self-assembly, slippage, supramolecular.

Role of mature leaves in inhibition of root bud growth inEuphorbia esulaL.

Weed Science ◽  
1999 ◽  
Vol 47 (5) ◽  
pp. 544-550 ◽  
Author(s):  
David P. Horvath
Keyword(s):  
Lateral Roots ◽  
Axillary Buds ◽  
Minor Effect ◽  
Correlative Inhibition ◽  
Auxin Transport Inhibitor ◽  
Naphthylphthalamic Acid ◽  
Bud Growth ◽  
A Minor ◽  
Root Buds

Earlier studies on the source of signals controlling correlative inhibition of root buds (underground adventitious buds located on the lateral roots) inEuphorbia esulaindicated that either growing meristems (apical or axillary buds) or fully expanded leaves could prevent root buds from breaking quiescence. An investigation of the production and transport requirements of the leaf-derived signal is described. As few as three leaves remaining on budless stems greatly reduced the growth of (but not the number of growing) root buds. Also, light and CO2fixation were necessary for the leaf effects on root bud growth, but not necessary for correlative inhibition imposed by growing axillary buds. Treatment of plants with Ametryn induced root bud growth on budless plants but not on plants with intact axillary buds. The polar auxin transport inhibitor N-1-naphthylphthalamic acid prevented transmission or the signal from growing axillary buds, but it had only a minor effect on the transmission of the leaf-derived signal. Treatment of plants with gibberellic acid (GA) induced growth of root buds under otherwise noninducing conditions to some extent in all plants. However, the greatest effects of GA were on plants with intact leaves (meristemless/budless and meristemless). GA had no significant effect on root bud quiescence under conditions that induced root bud growth.

Voltammetric investigation of the kinetics of alkali metal cation reduction in N,N-dimethylformamide

1975 ◽  
Vol 28 (2) ◽  
pp. 237 ◽  
Author(s):  
JW Diggle ◽  
AJ Parker ◽  
DA Owensby
Keyword(s):  
Electron Transfer ◽  
Alkali Metal ◽  
Propylene Carbonate ◽  
Rate Constant ◽  
Alkali Metal Cation ◽  
Electrode Reaction ◽  
Amalgam Electrode ◽  
Kinetics Of ◽  
Dipolar Aprotic Solvents

The standard electron-transfer heterogeneous rate constant of lithium, potassium, sodium and caesium amalgams in N,N-dimethylformamide was ascertained employing cyclic voltammetry in an effort to relate the presence of a non-equilibrium electrode reaction at the dropping lithium amalgam electrode to the variation of the lithium amalgam electrode potential with amalgam electrode con- figuration, i.e. whether streaming, dropping or stationary. Such variations are not observed at other alkali metal amalgam electrodes. ��� In the dipolar aprotic solvents the standard electron-transfer heterogeneous rate constant for the Li(Hg) electrode increases as the solvating power for Li+ decreases, i.e. dimethyl sulphoxide < di- methylformamide < propylene carbonate. Water is a much stronger solvator of Li+ than is propylene carbonate, but the electron transfer is faster in water than in propylene carbonate; the important role of entropic contributions in ion solvation is discussed as an explanation.

The role of sucrose concentration in self-assembly kinetics of high methoxyl pectin

2018 ◽  
Vol 112 ◽  
pp. 1183-1190 ◽  
Author(s):  
Daniela Giacomazza ◽  
Donatella Bulone ◽  
Pier Luigi San Biagio ◽  
Rosamaria Marino ◽  
Romano Lapasin
Keyword(s):  
Self Assembly ◽  
Sucrose Concentration ◽  
Assembly Kinetics ◽  
Kinetics Of

scholarly journals In-Depth Analysis of the Effect of Fragmentation on the Crystallization-Driven Self-Assembly Growth Kinetics of 1D Micelles Studied by Seed Trapping

Polymers ◽  
2021 ◽  
Vol 13 (18) ◽  
pp. 3122
Author(s):  
Gerald Guerin ◽  
Paul A. Rupar ◽  
Mitchell A. Winnik
Keyword(s):  
Growth Kinetics ◽  
Self Assembly ◽  
Growth Process ◽  
Elevated Temperatures ◽  
Polymer Chains ◽  
Exponential Law ◽  
Depth Analysis ◽  
Protein Fibrils ◽  
Polymer Fractionation ◽  
Kinetics Of

Studying the growth of 1D structures formed by the self-assembly of crystalline-coil block copolymers in solution at elevated temperatures is a challenging task. Like most 1D fibril structures, they fragment and dissolve when the solution is heated, creating a mixture of surviving crystallites and free polymer chains. However, unlike protein fibrils, no new nuclei are formed upon cooling and only the surviving crystallites regrow. Here, we report how trapping these crystallites at elevated temperatures allowed us to study their growth kinetics at different annealing times and for different amounts of unimer added. We developed a model describing the growth kinetics of these crystallites that accounts for fragmentation accompanying the 1D growth process. We show that the growth kinetics follow a stretched exponential law that may be due to polymer fractionation. In addition, by evaluating the micelle growth rate as a function of the concentration of unimer present in solution, we could conclude that the micelle growth occurred in the mononucleation regime.

α- and β-Cyclodextrin [2]rotaxanes with (diethylenetriamine)platinum(II) stoppers

2005 ◽  
Vol 83 (12) ◽  
pp. 2091-2097 ◽  
Author(s):  
Victor X Jin ◽  
Donal H Macartney ◽  
Erwin Buncel
Keyword(s):  
Self Assembly ◽  
Electrospray Mass Spectrometry ◽  
Platinum Complexes ◽  
H Nmr ◽  
Bridging Ligand ◽  
Dinuclear Platinum ◽  
End Groups ◽  
Group A ◽  
Kinetics Of ◽  
End Group

A series of dinuclear platinum(II) complexes, [(dien)Pt(NH2(CH2)nNH2)Pt(dien)]Cl4 (dien = diethylenetriamine, n = 8, 9, 10, and 12) and their corresponding [2]rotaxanes with α-cyclodextrin (α-CD), [(dien)Pt{NH2(CH2)nNH2·α-CD}Pt(dien)]Cl4, have been synthesized and characterized by 1H, 13C, and 195Pt NMR spectroscopy and electrospray mass spectrometry. The rotaxanes were prepared by reacting the {NH2(CH2)nNH2·α-CD} pseudorotaxanes with [Pt(dien)]Cl, to stopper the included linear α,ω-diaminoalkane chains with the inert Pt(II) end groups. The kinetics of the self-assembly and dissociation of the β-CD rotaxane, [(dien)Pt{NH2(CH2)10NH2·β-CD}Pt(dien)]4+, were investigated by using 1H NMR and are indicative of a slippage mechanism, owing to the comparable sizes of the β-CD cavity and the [Pt(dien)]+ end group. A relatively weak inclusion of the end group in the β-CD cavity precedes a thermally promoted passage of the β-CD over the [Pt(dien)]+ end group onto the hydrophobic polymethylene chain of the bridging ligand of the thread. Key words: rotaxanes, pseudorotaxanes, cyclodextrin, platinum complexes, slippage mechanism.

scholarly journals The Economics of Credence Goods: An Experiment on the Role of Liability, Verifiability, Reputation, and Competition

2011 ◽  
Vol 101 (2) ◽  
pp. 526-555 ◽  
Author(s):  
Uwe Dulleck ◽  
Rudolf Kerschbamer ◽  
Matthias Sutter
Keyword(s):  
Asymmetric Information ◽  
Minor Effect ◽  
Credence Goods ◽  
Yield Efficiency ◽  
A Minor

Credence goods markets are characterized by asymmetric information between sellers and consumers that may give rise to inefficiencies, such as under- and overtreatment or market breakdown. We study in a large experiment with 936 participants the determinants for efficiency in credence goods markets. While theory predicts that liability or verifiability yield efficiency, we find that liability has a crucial, but verifiability at best a minor, effect. Allowing sellers to build up reputation has little influence, as predicted. Seller competition drives down prices and yields maximal trade, but does not lead to higher efficiency as long as liability is violated. (JEL D12, D82)

scholarly journals In anemia of multiple myeloma, hepcidin is induced by increased bone morphogenetic protein 2

Blood ◽  
2010 ◽  
Vol 116 (18) ◽  
pp. 3635-3644 ◽  
Author(s):  
Ken Maes ◽  
Elizabeta Nemeth ◽  
G. David Roodman ◽  
Alissa Huston ◽  
Flavia Esteve ◽  
...  
Keyword(s):  
Multiple Myeloma ◽  
Bone Morphogenetic Proteins ◽  
Bone Morphogenetic Protein 2 ◽  
Minor Effect ◽  
Morphogenetic Protein ◽  
Huh7 Cells ◽  
Serum Hepcidin ◽  
Stimulatory Capacity ◽  
A Minor

Abstract Hepcidin is the principal iron-regulatory hormone and a pathogenic factor in anemia of inflammation. Patients with multiple myeloma (MM) frequently present with anemia. We showed that MM patients had increased serum hepcidin, which inversely correlated with hemoglobin, suggesting that hepcidin contributes to MM-related anemia. Searching for hepcidin-inducing cytokines in MM, we quantified the stimulation of hepcidin promoter-luciferase activity in HuH7 cells by MM sera. MM sera activated the hepcidin promoter significantly more than did normal sera. We then examined the role of bone morphogenetic proteins (BMPs) and interleukin-6 (IL-6), the major transcriptional regulators of hepcidin. Mutations in both BMP-responsive elements abrogated the activation dramatically, while mutations in the IL-6–responsive signal transducer and activator of transcription 3-binding site (STAT3-BS) had only a minor effect. Cotreatment with anti–BMP-2/4 or noggin-Fc blocked the promoter induction with all MM sera, anti–IL-6 blocked it with a minority of sera, whereas anti–BMP-4, -6, or -9 antibodies had no effect. BMP-2–immunodepleted MM sera had decreased promoter stimulatory capacity, and BMP-2 concentrations in MM sera were significantly higher than in normal sera. Our results demonstrate that BMP-2 is a major mediator of the hepcidin stimulatory activity of MM sera.

scholarly journals Effect of Surface Roughness on Aggregation of Polypeptide Chains: A Monte Carlo Study

Biomolecules ◽  
2021 ◽  
Vol 11 (4) ◽  
pp. 596
Author(s):  
Nguyen Truong Co ◽  
Mai Suan Li
Keyword(s):  
Surface Roughness ◽  
Self Assembly ◽  
Molecular Mechanisms ◽  
Monte Carlo Study ◽  
The Self ◽  
Living Organisms ◽  
Polypeptide Chains ◽  
The Impact ◽  
Kinetics Of

The self-assembly of amyloidogenic peptides and proteins into fibrillar structures has been intensively studied for several decades, because it seems to be associated with a number of neurodegenerative diseases, such as Alzheimer’s and Parkinson’s disease. Therefore, understanding the molecular mechanisms of this phenomenon is important for identifying an effective therapy for the corresponding diseases. Protein aggregation in living organisms very often takes place on surfaces like membranes and the impact of a surface on this process depends not only on the surface chemistry but also on its topology. Our goal was to develop a simple lattice model for studying the role of surface roughness in the aggregation kinetics of polypeptide chains and the morphology of aggregates. We showed that, consistent with the experiment, an increase in roughness slows down the fibril formation, and this process becomes inhibited at a very highly level of roughness. We predicted a subtle catalytic effect that a slightly rough surface promotes the self-assembly of polypeptide chains but does not delay it. This effect occurs when the interaction between the surface and polypeptide chains is moderate and can be explained by taking into account the competition between energy and entropy factors.

The role of isomerization in the kinetics of self-assembly: p-terphenyl-m-dicarbonitrile on the Ag(111) surface

2015 ◽  
Vol 17 (17) ◽  
pp. 11182-11192 ◽  
Author(s):  
David Abbasi-Pérez ◽  
J. Manuel Recio ◽  
Lev Kantorovich
Keyword(s):  
Self Assembly ◽  
Isomerization Mechanism ◽  
Kinetics Of

para-Terphenyl-meta-dicarbonitrile molecules diffuse by pivoting on the Ag(111) surface, and by means of the assisted isomerization mechanism self-assemble to form ribbons, linkers, clusters and brickwall islands.

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