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1.
Small ; 20(26): e2305684, 2024 Jun.
Article in English | MEDLINE | ID: mdl-38247186

ABSTRACT

Understanding the conformation of proteins in the nanoparticle corona has important implications in how organisms respond to nanoparticle-based drugs. These proteins coat the nanoparticle surface, and their properties will influence the nanoparticle's interaction with cell targets and the immune system. While some coronas are thought to be disordered, two key unanswered questions are the degree of disorder and solvent accessibility. Here, a model is developed for protein corona disorder in polystyrene nanoparticles of varying size. For two different proteins, it is found that binding affinity decreases as nanoparticle size increases. The stoichiometry of binding, along with changes in the hydrodynamic size, supports a highly solvated, disordered protein corona anchored at a small number of attachment sites. The scaling of the stoichiometry versus nanoparticle size is consistent with disordered polymer dimensions. Moreover, it is found that proteins are destabilized less in the presence of larger nanoparticles, and hydrophobic exposure decreases at lower curvatures. The observations hold for proteins on flat polystyrene surfaces, which have the lowest hydrophobic exposure. The model provides an explanation for previous observations of increased amyloid fibrillation rates in the presence of larger nanoparticles, and it may rationalize how cell receptors can recognize protein disorder in therapeutic nanoparticles.


Subject(s)
Nanoparticles , Polystyrenes , Protein Binding , Protein Corona , Polystyrenes/chemistry , Nanoparticles/chemistry , Protein Corona/chemistry , Solvents/chemistry , Hydrophobic and Hydrophilic Interactions , Particle Size
2.
J Biomol Struct Dyn ; 42(4): 2162-2169, 2024.
Article in English | MEDLINE | ID: mdl-37286380

ABSTRACT

G-quadruplexes (G4s) are secondary four-stranded DNA helical structures made up of guanine-rich nucleic acids that can assemble in the promoter regions of multiple genes under the appropriate conditions. Stabilization of G4 structures by small molecules can regulate transcription in non-telomeric regions, including in proto-oncogenes and promoter regions, contributing to anti-proliferative and anti-tumor activities. Because G4s are detectable in cancer cells but not in normal cells, they make excellent drug discovery targets. Diminazene, DMZ (or berenil), has been shown to be an efficient G-quadruplex binder. Due to the stability of the folding topology, G-quadruplex structures are frequently found in the promotor regions of oncogenes and may play a regulatory role in gene activation. Using molecular docking and molecular dynamics simulations on several different binding poses, we have studied DMZ binding toward multiple G4 topologies of the c-MYC G-quadruplex. DMZ binds preferentially to G4s that have extended loops and flanking bases. This preference arises from its interactions with the loops and the flanking nucleotides, which were not found in the structure lacking extended regions. The binding to the G4s with no extended regions instead occurred mostly through end stacking. All binding sites for DMZ were confirmed by 100 ns molecular dynamics simulations and through binding enthalpies calculated using the MM-PBSA method. The primary driving forces were electrostatic, as the cationic DMZ interacts with the anionic phosphate backbone, and through van der Waals interactions, which primarily contributed in end stacking interactions.Communicated by Ramaswamy H. Sarma.


Subject(s)
Diminazene/analogs & derivatives , G-Quadruplexes , Diminazene/chemistry , Diminazene/metabolism , Molecular Docking Simulation , DNA/chemistry
3.
Angew Chem Int Ed Engl ; 62(13): e202214855, 2023 03 20.
Article in English | MEDLINE | ID: mdl-36722146

ABSTRACT

Shortwave infrared (SWIR) dyes are characterized by their ability to absorb light from 900 to 1400 nm, which is ideal for deep tissue imaging owing to minimized light scattering and interference from endogenous pigments. An approach to access such molecules is to tune the photophysical properties of known near-infrared dyes. Herein, we report the development of a series of easily accessible (three steps) SWIR xanthene dyes based on a dibenzazepine donor conjugated to thiophene (SCR-1), thienothiophene (SCR-2), or bithiophene (SCR-3). We leverage the fact that SCR-1 undergoes a bathochromic shift when aggregated for in vivo studies by developing a ratiometric nanoparticle for NO (rNP-NO), which we employed to successfully visualize pathological levels of nitric oxide in a drug-induced liver injury model via deep tissue SWIR photoacoustic (PA) imaging. Our work demonstrates how easily this dye series can be utilized as a component in nanosensor designs for imaging studies.


Subject(s)
Nitric Oxide , Photoacoustic Techniques , Photoacoustic Techniques/methods , Xanthenes , Diagnostic Imaging/methods , Fluorescent Dyes , Optical Imaging
4.
Org Lett ; 23(19): 7640-7644, 2021 10 01.
Article in English | MEDLINE | ID: mdl-34550707

ABSTRACT

Few xanthene-based near-infrared (NIR) photoacoustic (PA) dyes with absorbance >800 nm exist. As accessibility to these dyes requires long and tedious synthetic steps, we designed a NIR dye (XanthCR-880) with thienylpiperidine donors and a xanthene acceptor that is accessible in 3-4 synthetic steps. The dye boasts a strong PA signal at 880 nm with good biological compatibility and photostability, yields multiplexed imaging with an aza-BODIPY reference dye, and is detected at a depth of 4 cm.


Subject(s)
Benzopyrans/chemistry , Boron Compounds/chemistry , Fluorescent Dyes/chemistry , Xanthenes/chemistry , Molecular Structure , Photoacoustic Techniques/methods
5.
J Org Chem ; 85(19): 12108-12116, 2020 10 02.
Article in English | MEDLINE | ID: mdl-32829632

ABSTRACT

An effective design strategy with an efficient synthetic route to xanthene-based far-red to near-infrared dyes is reported. The dyes were prepared by the Suzuki cross-coupling of the electron-poor fluorescein ditriflate with the electron-rich boronic acid/ester-functionalized pyrrole (2C/3C) and indole (2D/3D) moieties. Upon treatment with trifluoroacetic acid, the closed nonfluorescent forms of the dyes (2C and 2D) ring-opened to their fluorescent forms (3C and 3D). The absorption maxima were 665 and 704 nm, while the emission maxima were 717 and 719 nm for 3C and 3D, respectively. The closed forms of the dyes were soluble in chloroform and acetonitrile. To test the efficacy of the dyes as probes, a turn-off fluoride ion probe was prepared from 3C, which consisted of a silyl ester receptor. The probe responded strongly to low concentrations of fluoride, carbonate, and acetate ions, weakly to phosphate ions, but not to the other halogens. Moreover, the probe can detect the minimum concentration of F- in water.

6.
J Biomol Struct Dyn ; 37(5): 1346-1359, 2019 Mar.
Article in English | MEDLINE | ID: mdl-29629830

ABSTRACT

Continuum finite element material models used for traumatic brain injury lack local injury parameters necessitating nanoscale mechanical injury mechanisms be incorporated. One such mechanism is membrane mechanoporation, which can occur during physical insults and can be devastating to cells, depending on the level of disruption. The current study investigates the strain state dependence of phospholipid bilayer mechanoporation and failure. Using molecular dynamics, a simplified membrane, consisting of 72 1-palmitoyl-2-oleoyl-phosphatidylcholine (POPC) phospholipids, was subjected to equibiaxial, 2:1 non-equibiaxial, 4:1 non-equibiaxial, strip biaxial, and uniaxial tensile deformations at a von Mises strain rate of 5.45 × 108 s-1, resulting in velocities in the range of 1 to 4.6 m·s-1. A water bridge forming through both phospholipid bilayer leaflets was used to determine structural failure. The stress magnitude, failure strain, headgroup clustering, and damage responses were found to be strain state-dependent. The strain state order of detrimentality in descending order was equibiaxial, 2:1 non-equibiaxial, 4:1 non-equibiaxial, strip biaxial, and uniaxial. The phospholipid bilayer failed at von Mises strains of .46, .47, .53, .77, and 1.67 during these respective strain path simulations. Additionally, a Membrane Failure Limit Diagram (MFLD) was created using the pore nucleation, growth, and failure strains to demonstrate safe and unsafe membrane deformation regions. This MFLD allowed representative equations to be derived to predict membrane failure from in-plane strains. These results provide the basis to implement a more accurate mechano-physiological internal state variable continuum model that captures lower length scale damage and will aid in developing higher fidelity injury models.


Subject(s)
Biomechanical Phenomena , Lipid Bilayers/chemistry , Molecular Dynamics Simulation , Phosphatidylcholines/chemistry , Algorithms , Models, Theoretical , Phospholipids/chemistry
7.
J Phys Chem A ; 122(49): 9572-9578, 2018 Dec 13.
Article in English | MEDLINE | ID: mdl-30398872

ABSTRACT

An interatomic potential for sulfur has been developed using the bond order addition to the modified embedded-atom method (MEAM-BO). In order to correctly model the interaction between molecules, dispersion forces have been included via the DFT-D3 modification. It is demonstrated that this semiempirical classical potential correctly reproduces the behavior of the S2 dimer, various cyclic sulfur rings, the molecular solids α-, ß-, and γ-sulfur, and a number of theoretical, high symmetry sulfur structures. This potential will serve as a useful tool in the atomistic modeling of sulfur and, ultimately, in the modeling of sulfur containing organic compounds using this updated MEAM-BO formalism.

8.
J Phys Chem A ; 121(7): 1502-1524, 2017 Feb 23.
Article in English | MEDLINE | ID: mdl-28121152

ABSTRACT

In this paper, we develop a new modified embedded atom method (MEAM) potential that includes the bond order (MEAM-BO) to describe the energetics of unsaturated hydrocarbons (double and triple carbon bonds) and also develop improved parameters for saturated hydrocarbons from those of our previous work. Such quantities like bond lengths, bond angles, and atomization energies at 0 K, dimer molecule interactions, rotational barriers, and the pressure-volume-temperature relationships of dense systems of small molecules give a comparable or more accurate property relative to experimental and first-principles data than the classical reactive force fields REBO and ReaxFF. Our extension of the MEAM potential for unsaturated hydrocarbons (MEAM-BO) is a step toward developing more reliable and accurate polymer simulations with their associated structure-property relationships, such as reactive multicomponent (organic/metal) systems, polymer-metal interfaces, and nanocomposites. When the constants for the BO are zero, MEAM-BO reduces to the original MEAM potential. As such, this MEAM-BO potential describing the interaction of organic materials with metals within the same MEAM formalism is a significant advancement for computational materials science.

9.
Toxicol Sci ; 143(1): 46-53, 2015 Jan.
Article in English | MEDLINE | ID: mdl-25304213

ABSTRACT

Paraoxonase 1 (PON1) is a calcium-dependent hydrolase associated with serum high-density lipoprotein particles. PON1 hydrolyzes some organophosphates (OPs), including some nerve agents, through nucleophilic attack of hydroxide ion (from water) in the active site. Most OPs are hydrolyzed inefficiently. This project seeks to identify nucleophiles that can enhance PON1-mediated OP degradation. A series of novel nucleophiles, substituted phenoxyalkyl pyridinium oximes, has been synthesized which enhance the degradation of surrogates of sarin (nitrophenyl isopropyl methylphosphonate; NIMP) and VX (nitrophenyl ethyl methylphosphonate; NEMP). Two types of in vitro assays have been conducted, a direct assay using millimolar concentrations of substrate with direct spectrophotometric quantitation of a hydrolysis product (4-nitrophenol) and an indirect assay using submicromolar concentrations of substrate with quantitation by the level of inhibition of an exogenous source of acetylcholinesterase from non-hydrolyzed substrate. Neither NIMP nor NEMP is hydrolyzed effectively by PON1 if one of these novel oximes is absent. However, in the presence of eight novel oximes, PON1-mediated degradation of both surrogates occurs. Computational modeling has created a model of PON1 embedded in phospholipid and has indicated general agreement of the binding enthalpies with the relative efficacy as PON1 enhancers. PON1 enhancement of degradation of OPs could be a unique and unprecedented mechanism of antidotal action.


Subject(s)
Antidotes/pharmacology , Aryldialkylphosphatase/blood , Enzyme Activators/pharmacology , Organothiophosphorus Compounds/metabolism , Oximes/pharmacology , Pyridinium Compounds/pharmacology , Sarin/metabolism , Catalytic Domain , Enzyme Activation , Humans , Hydrolysis , Hydroxides/metabolism , Inactivation, Metabolic , Molecular Dynamics Simulation , Nitrophenols/metabolism , Sarin/analogs & derivatives , Spectrophotometry , Water/metabolism
10.
J Inorg Organomet Polym Mater ; 24(1): 241-249, 2014 Jan 01.
Article in English | MEDLINE | ID: mdl-24611036

ABSTRACT

The structures and stabilities of a series of endohedral gold clusters containing ten gold atoms M@Au10 (M = W, Mo, Ru, Co) have been determined using density functional theory. The gradient-corrected functional BP86, the Tao-Perdew-Staroverov-Scuseria TPSS meta-GGA functional, and the hybrid density functionals B3LYP and PBE1PBE were employed to calculate the structures, binding energies, adiabatic ionization potentials, and adiabatic electron affinities for these clusters. The LanL2DZ effective core potentials and the corresponding valence basis sets were employed. The M@Au10 (M = W, Mo, Ru, Co) clusters have higher binding energies than an empty Au10 cluster. In addition, the large HOMO-LUMO gaps suggest that the M@Au10 (M = W, Mo, Ru, Co) clusters are all likely to be stable chemically. The ionization potentials and electron affinities for these clusters are very high, and the W@Au10 and Mo@Au10 clusters have electron affinities similar to the super-halogen Al13.

11.
BMC Bioinformatics ; 13 Suppl 15: S13, 2012.
Article in English | MEDLINE | ID: mdl-23046347

ABSTRACT

BACKGROUND: Currently, the tandem mass spectrometry (MSMS) of peptides is a dominant technique used to identify peptides and consequently proteins. The peptide fragmentation inside the mass analyzer typically offers a spectrum containing several different groups of ions. The mass to charge (m/z) values of these ions can be exactly calculated following simple rules based on the possible peptide fragmentation reactions. But the (relative) intensities of the particular ions cannot be simply predicted from the amino-acid sequence of the peptide. This study presents initial work towards developing a theoretical fundamental approach to ion intensity elucidation by utilizing quantum mechanical computations. METHODS: MSMS spectra of the doubly charged GAVLK peptide were collected on electrospray ion trap mass spectrometers using low energy modes of fragmentation. Density functional theory (DFT) calculations were performed on the population of ion precursors to determine the fragment ion intensities corresponding to a Boltzmann distribution of the protonation of nitrogens in the peptide backbone amide bonds. RESULTS: We were able to a) predict the y and b ions intensities order in concert with the experimental observation; b) predict relative intensities of y ions with errors not exceeding the experimental variation. CONCLUSIONS: These results suggest that the GAVLK peptide fragmentation process in the ion trap mass spectrometer is predominantly driven by the thermodynamic stability of the precursor ions formed upon ionization of the sample. The computational approach presented in this manuscript successfully calculated ion intensities in the mass spectra of this doubly charged tryptic peptide, based solely on its amino acid sequence. As such, this work indicates a potential of incorporating quantum mechanical calculations into mass spectrometry based algorithms for molecular identification.


Subject(s)
Computational Biology/methods , Ions/chemistry , Peptides/chemistry , Tandem Mass Spectrometry/methods , Algorithms , Amino Acid Sequence , Thermodynamics
12.
J Mol Model ; 18(6): 2869-83, 2012 Jun.
Article in English | MEDLINE | ID: mdl-22127613

ABSTRACT

Carboxylesterases (CEs) are ubiquitous enzymes responsible for the detoxification of xenobiotics. In humans, substrates for these enzymes are far-ranging, and include the street drug heroin and the anticancer agent irinotecan. Hence, their ability to bind and metabolize substrates is of broad interest to biomedical science. In this study, we focused our attention on dynamic motions of a CE from B. subtilis (pnbCE), with emphasis on the question of what individual domains of the enzyme might contribute to its catalytic activity. We used a 10 ns all-atom molecular dynamics simulation, normal mode calculations, and enzyme kinetics to understand catalytic consequences of structural changes within this enzyme. Our results shed light on how molecular motions are coupled with catalysis. During molecular dynamics, we observed a distinct C-C bond rotation between two conformations of Glu310. Such a bond rotation would alternately facilitate and impede protonation of the active site His399 and act as a mechanism by which the enzyme alternates between its active and inactive conformation. Our normal mode results demonstrate that the distinct low-frequency motions of two loops in pnbCE, coil_5 and coil_21, are important in substrate conversion and seal the active site. Mutant CEs lacking these external loops show significantly reduced rates of substrate conversion, suggesting this sealing motion prevents escape of substrate. Overall, the results of our studies give new insight into the structure-function relationship of CEs and have implications for the entire family of α/ß fold family of hydrolases, of which this CE is a member.


Subject(s)
Bacillus subtilis/enzymology , Bacterial Proteins/chemistry , Carboxylesterase/chemistry , Molecular Dynamics Simulation , Algorithms , Amino Acid Sequence , Amino Acid Substitution , Bacterial Proteins/genetics , Biocatalysis , Carboxylesterase/genetics , Catalytic Domain , Hydrogen Bonding , Hydrolysis , Kinetics , Molecular Sequence Data , Mutagenesis, Site-Directed , Protein Binding , Protein Structure, Secondary , Thermodynamics
13.
Environ Sci Technol ; 44(2): 668-74, 2010 Jan 15.
Article in English | MEDLINE | ID: mdl-20000674

ABSTRACT

Abiotic transformation of triclosan (TCS) was investigated by incubating TCS with Fe(III)- and Na-montmorillonite at 40% relative humidity and room temperature for up to 100 days. The TCS transformation products were characterized using LC/MS, GC/MS, and computational modeling and quantified using HPLC/UV and GC/MS. Within 1-5 days, depending on the initial TCS concentrations, about 55% of the TCS was rapidly transformed in the presence of Fe(III)-montmorillonite, producing 2,4-dichlorophenol, 3-chlorophenol, 2,4-dichlorophenol dimer, chlorophenoxy phenols, and TCS dimers and trimers. Computational modeling based on density functional theory confirmed the formation of four TCS dimer conformers and six TCS trimer conformers. The TCS phenoxy radicals, produced by Fe(III) oxidation of TCS, react with other TCS molecules to form TCS dimers. The TCS trimers were formed by attachment of TCS dimer phenoxy radicals, produced by Fe(III) oxidation of TCS dimers, with TCS molecules. Significantly smaller quantities of TCS transformation products were detected in the reactions with Na-montmorillonite compared to the reactions with Fe(III)-montmorillonite. Formation of a significant amount of 2,4-dichlorophenol, especially in reaction with Fe(III)-montmorillonite, may have negative impact on the environment because of its toxicity. However, mineral-facilitated TCS polymerization may reduce its mobility and bioavailability in soils.


Subject(s)
Bentonite/chemistry , Environmental Pollutants/chemistry , Fatty Acid Synthesis Inhibitors/chemistry , Iron/chemistry , Triclosan/chemistry , Molecular Structure , Time Factors
14.
Biol Chem ; 389(2): 149-62, 2008 Feb.
Article in English | MEDLINE | ID: mdl-18163883

ABSTRACT

Abstract Structures of mammalian carboxylesterases (CEs) reveal the presence of a 'side door' that is proposed to act as an alternative pore for the trafficking of substrates and products. p-Nitrobenzyl esterase (pnb CE) from Bacillus subtilis exhibits close structural homology and a similar side-door domain as mammalian CEs. We investigated the role of a specific 'gate' residue at the side door (i.e., Leu 362) during pnb CE-catalyzed hydrolysis of model esters, pesticides, and lipids. Recombinant pnb CE proteins containing mutations at position 362 demonstrated markedly lower kcat and kcat/Km values. The mutation with the most significant impact on catalysis was the L362R mutant (kcat/Km was 22-fold lower). Moreover, the ability of the L362R mutant to be inhibited by organophosphates (OP) was also lower. Investigation into the altered catalytic proficiency using pH-activity studies indicated that the catalytic triad of the mutant enzyme was preserved. Furthermore, viscosity variation and carbamate inhibition experiments indicated that rates of substrate association and acylation/deacylation were lower. Finally, recombinant CEs were found to possess lipolytic activity toward cholesteryl oleate and 2-arachidonylglycerol. In summary, the L362R mutant CE markedly slowed the rate of ester hydrolysis and was less sensitive to OP inhibition. The apparent causes of the diminished catalysis are discussed.


Subject(s)
Bacillus subtilis/enzymology , Carboxylic Ester Hydrolases/chemistry , Carboxylic Ester Hydrolases/metabolism , Binding Sites , Catalysis , Esters/metabolism , Kinetics , Lipid Metabolism , Mutation, Missense , Pesticides/metabolism , Protein Structure, Tertiary
15.
Phys Chem Chem Phys ; 8(27): 3172-91, 2006 Jul 21.
Article in English | MEDLINE | ID: mdl-16902710

ABSTRACT

Advances in theory and algorithms for electronic structure calculations must be incorporated into program packages to enable them to become routinely used by the broader chemical community. This work reviews advances made over the past five years or so that constitute the major improvements contained in a new release of the Q-Chem quantum chemistry package, together with illustrative timings and applications. Specific developments discussed include fast methods for density functional theory calculations, linear scaling evaluation of energies, NMR chemical shifts and electric properties, fast auxiliary basis function methods for correlated energies and gradients, equation-of-motion coupled cluster methods for ground and excited states, geminal wavefunctions, embedding methods and techniques for exploring potential energy surfaces.


Subject(s)
Algorithms , Biophysics/methods , Quantum Theory , Cluster Analysis , Electrons , Magnetic Resonance Spectroscopy , Models, Chemical , Thermodynamics
16.
J Chem Phys ; 124(11): 114107, 2006 Mar 21.
Article in English | MEDLINE | ID: mdl-16555874

ABSTRACT

We have formulated a second-order perturbative correction for perfect-pairing wave functions [PP2] based on similarity-transformed perturbation techniques in coupled cluster theory. The perfect-pairing approximation is used to obtain a simple reference wave function which can qualitatively describe bond breaking, diradicals, and other highly correlated systems, and the perturbative correction accounts for the dynamical correlation. An efficient implementation of this correction using the resolution of the identity approximation enables PP2 to be computed at a cost only a few times larger than that of canonical MP2 for systems with hundreds of active electrons and tens of heavy atoms. PP2 significantly improves on MP2 predictions in various systems with a challenging electronic structure.

17.
J Phys Chem A ; 110(7): 2434-9, 2006 Feb 23.
Article in English | MEDLINE | ID: mdl-16480302

ABSTRACT

We report time-dependent density functional theory calculations of the vertical excitation energies for the singlet states of three-coordinate 5H-dibenzoborole (DBB) derivatives and four-coordinate 5-fluoro-5H-dibenzoborole ion (FDBB) derivatives. These molecules show remarkable hypsochromic (blue) shifts in their fluorescence spectra and bathochromic (red) shifts in their absorption spectra when the bridging boron atoms change their coordination number from three to four. We constructed a series of derivatives of DBB and FDBB and studied how the energies of the electronic excitations change. The states with prominent oscillator strength in all of the DBB and FDBB derivatives show similar shifts of their excitation energies upon coordination. The three-coordinate DBB derivative 5-(2,4,6-triisopropylphenyl)-2,8-dimethoxy-3,7-bis[p-(N,N-diphenylamino)phenyl]-5H-dibenzo[d,b]borole has an intense absorption at 3.25 eV, which shifts in the four-coordinate FDBB derivative 5-fluro-5-(2,4,6-triisopropylphenyl)-2,8-dimethoxy-3,7-bis[p-(N,N-dip henylamino)phenyl]-5H-dibenzo[d,b]borole ion to 3.17 eV. The experimental absorption peaks are 3.43 and 3.31 eV, respectively. In addition, we investigated and analyzed the nature of these electronic excitations using attachment/detachment density plots, with which we characterized the changes in electron density that arose from the excitations.


Subject(s)
Algorithms , Boron Compounds/chemistry , Electrons , Energy Transfer , Models, Molecular , Molecular Structure , Spectrum Analysis
18.
J Am Chem Soc ; 125(11): 3273-83, 2003 Mar 19.
Article in English | MEDLINE | ID: mdl-12630883

ABSTRACT

The highly disparate rates of aromatic nitrosation and nitration, despite the very similar (electrophilic) properties of the active species: NO(+) and NO(2)(+) in Chart 1, are quantitatively reconciled. First, the thorough mappings of the potential-energy surfaces by high level (ab initio) molecular-orbital methodologies involving extensive coupled-cluster CCSD(T)/6-31G optimizations establish the intervention of two reactive intermediates in nitration (Figure 8) but only one in nitrosation (Figure 7). Second, the same distinctive topologies involving double and single potential-energy minima (Figures 6 and 5) also emerge from the semiquantitative application of the Marcus-Hush theory to the transient spectral data. Such a striking convergence from quite different theoretical approaches indicates that the molecular-orbital and Marcus-Hush (potential-energy) surfaces are conceptually interchangeable. In the resultant charge-transfer mechanism, the bimolecular interactions of arene donors with both NO(+) and NO(2)(+) spontaneously lead (barrierless) to pi-complexes in which electron transfer is concurrent with complexation. Such a pi-complex in nitration is rapidly converted to the sigma-complex, whereas this Wheland adduct in nitrosation merely represents a high energy (transition-state) structure. Marcus-Hush analysis thus demonstrates how the strongly differentiated (arene) reactivities toward NO(+) and NO(2)(+) can actually be exploited in the quantitative development of a single coherent (electron-transfer) mechanism for both aromatic nitrosation and nitration.

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