A Preference for Edgewise Interactions between Aromatic Rings and Carboxylate Anions:  The Biological Relevance of Anion−Quadrupole Interactions

2007 ◽  
Vol 111 (28) ◽  
pp. 8242-8249 ◽  
Author(s):  
Michael R. Jackson ◽  
Robert Beahm ◽  
Suman Duvvuru ◽  
Chandrasegara Narasimhan ◽  
Jun Wu ◽  
...  
Keyword(s):  
Aromatic Rings ◽  
Quadrupole Interactions ◽  
Biological Relevance ◽  
Carboxylate Anions

Reversible Inhibition of the Esterase Activity of Carboxypeptidase A by Carboxylate Anions

1973 ◽  
Vol 51 (16) ◽  
pp. 2639-2649 ◽  
Author(s):  
John W. Bunting ◽  
Chester D. Myers
Keyword(s):  
Competitive Inhibition ◽  
Hydrophobic Interactions ◽  
Enzyme Inhibitor ◽  
Inhibition Kinetics ◽  
Aromatic Rings ◽  
Carboxypeptidase A ◽  
Phenyllactic Acid ◽  
Reversible Inhibition ◽  
Mixed Inhibition ◽  
Carboxylate Anions

Reversible inhibition of the hydrolysis of O-(hippuryl)-L-3-phenyllactic acid by carboxypeptidase A has been studied for 26 carboxylate ion inhibitors at 25°, pH 7.5, and ionic strength 0.2 (NaCl). Competitive inhibition, partially competitive inhibition, and mixed inhibition kinetics were observed. Within homologous series, strictly competitive inhibition by the lower members gave way to partially competitive inhibition with higher members, while homologs having very large hydrocarbon moieties displayed mixed inhibition kinetics. Partially competitive inhibition in this system is not consistent with a scheme involving only 1:1 enzyme–inhibitor complexes; rather, higher order enzyme–inhibitor complexes will be necessary for a complete description of the inhibition mechanism.Inhibition constants (log Ki) for the aliphatic carboxylate ions which are strictly competitive inhibitors, are closely correlated linearly with Hansch's π-parameter for hydrophobicity. This quantitatively confirms the importance of hydrophobic interactions between carboxypeptidase A and inhibiting ions. Carboxylate ions containing aromatic rings are less effective inhibitors than expected on the basis of the π-parameters of their hydrocarbon moieties. The dependence of log Ki on π in this system is unusually strong for a binding phenomenon, and suggests that an inhibitor-dependent conformational change may also be involved.

Chemical and orientational imaging of polymeric samples

1994 ◽  
Vol 52 ◽  
pp. 68-69
Author(s):  
H. Ade ◽  
B. Hsiao ◽  
G. Mitchell ◽  
E. Rightor ◽  
A. P. Smith ◽  
...  
Keyword(s):  
Ethylene Terephthalate ◽  
National Laboratory ◽  
Brookhaven National Laboratory ◽  
Carbonyl Groups ◽  
Aromatic Rings ◽  
Edge Structure ◽  
X Ray ◽  
Scanning Transmission ◽  
Polymeric Samples ◽  
X Ray Absorption

We have used the Scanning Transmission X-ray Microscope at beamline X1A (X1-STXM) at Brookhaven National Laboratory (BNL) to acquire high resolution, chemical and orientation sensitive images of polymeric samples as well as point spectra from 0.1 μm areas. This sensitivity is achieved by exploiting the X-ray Absorption Near Edge Structure (XANES) of the carbon K edge. One of the most illustrative example of the chemical sensitivity achievable is provided by images of a polycarbonate/pol(ethylene terephthalate) (70/30 PC/PET) blend. Contrast reversal at high overall contrast is observed between images acquired at 285.36 and 285.69 eV (Fig. 1). Contrast in these images is achieved by exploring subtle differences between resonances associated with the π bonds (sp hybridization) of the aromatic groups of each polymer. PET has a split peak associated with these aromatic groups, due to the proximity of its carbonyl groups to its aromatic rings, whereas PC has only a single peak.

Reactions of an Aluminium(I) Reagent with 1,2-, 1,3- and 1,5-Dienes: Dearomatisation, Reversibility, and a Pericyclic Mechanism

2019 ◽  
Author(s):  
Clare Bakewell ◽  
Martí Garçon ◽  
Richard Y Kong ◽  
Louisa O'Hare ◽  
Andrew J. P. White ◽  
...  
Keyword(s):  
Reaction Mechanism ◽  
Dft Calculations ◽  
Transition State ◽  
Reaction Pathways ◽  
Aromatic Rings ◽  
Aromatic Character ◽  
Pericyclic Reaction

The reactions of an aluminium(I) reagent with a series of 1,2-, 1,3- and 1,5-dienes are reported. In the case of 1,3-dienes the reaction occurs by a pericyclic reaction mechanism, specifically a cheletropic cycloaddition, to form aluminocyclopentene containing products. This mechanism has been interrogated by stereochemical experiments and DFT calculations. The stereochemical experiments show that the (4+1) cycloaddition follows a suprafacial topology, while calculations support a concerted albeit asynchronous pathway in which the transition state demonstrates aromatic character. Remarkably, the substrate scope of the (4+1) cycloaddition includes dienes that are either in part, or entirely, contained within aromatic rings. In these cases, reactions occur with dearomatisation of the substrate and can be reversible. In the case of 1,2- or 1,5-dienes complementary reactivity is observed; the orthogonal nature of the C=C π-bonds (1,2-diene) and the homoconjugated system (1,5-diene) both disfavour a (4+1) cycloaddition. Rather, reaction pathways are determined by an initial (2+1) cycloaddition to form an aluminocyclopropane intermediate which can in turn undergo insertion of a further C=C π-bond leading to complex organometallic products that incorporate fused hydrocarbon rings.

Tandem Mass Spectrometric Evaluation of Core Structures of Aromatic Compounds after Catalytic Deoxygenation

2017 ◽  
Author(s):  
Xueming Dong
Keyword(s):  
Aromatic Compounds ◽  
Supported Catalyst ◽  
Mass Spectrometric ◽  
Spectrometric Method ◽  
Mass Spectrometric Method ◽  
Aromatic Rings ◽  
Tandem Mass Spectrometric ◽  
Catalytic Deoxygenation ◽  
Oxygen Atoms

Catalytic deoxygenation of coal enhances the stability and combustion performance of coal-derived liquids. However, determination of the selectivity of removal of oxygen atoms incorporated in or residing outside of aromatic rings is challenging. This limits the ability to evaluate the success of catalytic deoxygenation processes. A mass spectrometric method, in-source collision-activated dissociation (ISCAD), combined with high resolution product ion detection, is demonstrated to allow the determination of whether the oxygen atoms in aromatic compounds reside outside of aromatic rings or are part of the aromatic system, because alkyl chains can be removed from aromatic cores via ISCAD. Application of this method for the analysis of a subbituminous coal treated using a supported catalyst revealed that the catalytic treatment reduced the number of oxygen-containing heteroaromatic rings but not the number of oxygen atoms residing outside the aromatic rings.<br>

Tandem Mass Spectrometric Evaluation of Core Structures of Aromatic Compounds after Catalytic Deoxygenation

2017 ◽  
Author(s):  
Xueming Dong
Keyword(s):  
Aromatic Compounds ◽  
Supported Catalyst ◽  
Mass Spectrometric ◽  
Spectrometric Method ◽  
Mass Spectrometric Method ◽  
Aromatic Rings ◽  
Tandem Mass Spectrometric ◽  
Catalytic Deoxygenation ◽  
Oxygen Atoms

Catalytic deoxygenation of coal enhances the stability and combustion performance of coal-derived liquids. However, determination of the selectivity of removal of oxygen atoms incorporated in or residing outside of aromatic rings is challenging. This limits the ability to evaluate the success of catalytic deoxygenation processes. A mass spectrometric method, in-source collision-activated dissociation (ISCAD), combined with high resolution product ion detection, is demonstrated to allow the determination of whether the oxygen atoms in aromatic compounds reside outside of aromatic rings or are part of the aromatic system, because alkyl chains can be removed from aromatic cores via ISCAD. Application of this method for the analysis of a subbituminous coal treated using a supported catalyst revealed that the catalytic treatment reduced the number of oxygen-containing heteroaromatic rings but not the number of oxygen atoms residing outside the aromatic rings.<br>

A Chemical Perspective to the Anti-Amyloid Action of Compounds and a Nanoparticle Based Assay for Screening Amyloid Inhibitors

2020 ◽  
Author(s):  
Nidhi Gour ◽  
Bharti Koshti
Keyword(s):  
Memory Loss ◽  
Cost Effective ◽  
Structural Motif ◽  
Rapid Screening ◽  
Stacking Interactions ◽  
Aromatic Rings ◽  
Amyloid Fibers ◽  
Aromatic Stacking ◽  
Cost Effective Technique ◽  
The Brain

Aggregation of amyloid beeta 1-42 (Aβ<sub>42</sub>) peptide causes the formation of clustered deposits knows as amyloid plaques in the brain which leads to neuronal dysfunction and memory loss and associated with many neurological disorders including Alzheimer’s and Parkinson’s. Aβ<sub>42</sub> has core structural motif with phenylalanine at the 19 and 20 positions. The diphenylalanine (FF) residue plays a crucial role in the formation of amyloid fibers and serves as model peptide for studying Aβ<sub>42 </sub>aggregation. FF self-assembles to well-ordered tubular morphology via aromatic pi-pi stackings. Our studies, suggest that the aromatic rings present in the anti-amyloidogenic compounds may interact with the pi-pi stacking interactions present in the FF. Even the compounds which do not have aromatic rings, like cyclodextrin and cucurbituril show anti-amyloid property due to the binding of aromatic ring inside the guest cavity. Hence, our studies also suggest that compounds which may have a functional moiety capable of interacting with the aromatic stacking interactions might be tested for their anti-amyloidogenic properties. Further, in this manuscript, we have proposed two novel nanoparticle based assays for the rapid screening of amyloid inhibitors. In the first assay, interaction between biotin-tagged FF peptide and the streptavidin labelled gold nanoparticles (s-AuNPs) were used. In another assay, thiol-Au interactions were used to develop an assay for detection of amyloid inhibitors. It is envisaged that the proposed analytical method will provide a simple, facile and cost effective technique for the screening of amyloid inhibitors and may be of immense practical implications to find the therapeutic remedies for the diseases associated with the protein aggregation.

Low Molecular Weight Microfibers with Light Sensing Properties

2017 ◽  
Vol 54 (4) ◽  
pp. 655-658
Author(s):  
Andrei Bejan ◽  
Dragos Peptanariu ◽  
Bogdan Chiricuta ◽  
Elena Bicu ◽  
Dalila Belei
Keyword(s):  
Molecular Weight ◽  
Low Molecular Weight ◽  
X Ray Diffraction ◽  
Aromatic Rings ◽  
X Ray ◽  
Force Microscopy ◽  
Light Sensing ◽  
Sensing Applications ◽  
Atomic Force ◽  
Low Molecular Weight Compounds

Microfibers were obtained from organic low molecular weight compounds based on heteroaromatic and aromatic rings connected by aliphatic spacers. The obtaining of microfibers was proved by scanning electron microscopy. The deciphering of the mechanism of microfiber formation has been elucidated by X-ray diffraction, infrared spectroscopy, and atomic force microscopy measurements. By exciting with light of different wavelength, florescence microscopy revealed a specific optical response, recommending these materials for light sensing applications.

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