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1.
Brain Sci ; 13(1)2022 Dec 28.
Article in English | MEDLINE | ID: mdl-36672039

ABSTRACT

Recent studies have demonstrated that the brain activity of a group of people can be used to forecast choices at the population level. In this study, we attempted to neuroforecast aggregate consumer behavior of Internet users. During our electroencephalography (EEG) and eye-tracking study, participants were exposed to 10 banners that were also used in the real digital marketing campaign. In the separate online study, we additionally collected self-reported preferences for the same banners. We explored the relationship between the EEG, eye-tracking, and behavioral indexes obtained in our studies and the banners' aggregate efficiency provided by the large food retailer based on the decisions of 291,301 Internet users. An EEG-based engagement index (central beta/alpha ratio) significantly correlated with the aggregate efficiency of banners. Furthermore, our multiple linear regression models showed that a combination of eye-tracking, EEG and behavioral measurements better explained the market-level efficiency of banner advertisements than each measurement alone. Overall, our results confirm that neural signals of a relatively small number of individuals can forecast aggregate behavior at the population level.

2.
J Phys Chem A ; 121(36): 6727-6731, 2017 Sep 14.
Article in English | MEDLINE | ID: mdl-28809117

ABSTRACT

The cyclopentazolate anion, N5-, has been researched extensively over the years and detected in the gas phase more than a decade ago, but was only recently measured in solution. The process whereby aryl pentazole reduction leads to the production of N5- is still not fully understood. Here, the production of N5- in solution was investigated using isotopic labeling techniques while implementing changes to the synthesis methodologies. 15N labeled phenyl pentazole produced appropriately labeled phenyl pentazole radical anions and N5- which, upon collision induced dissociation, produced the expected N3- signals. Changing to higher purity solvent and less coated Na metal allowed for a much more rapid pace, with experiments taking less time. However, the best yields were obtained with heavily coated metal and much longer reaction times. Utilization of a vacuum line and ultrapure solvents led to no products being detected, indicating the importance of a sodium passivation layer in this reaction and the possibility that sodium is too strong a reducer. These findings can lead to better production methods of N5- and also explain past failures in implementing aryl pentazole reduction techniques.

3.
Angew Chem Int Ed Engl ; 55(42): 13233-13235, 2016 10 10.
Article in English | MEDLINE | ID: mdl-27385080

ABSTRACT

Compelling evidence has been found for the formation and direct detection of the cyclopentazole anion (cyclo-N5- ) in solution. The anion was prepared from phenylpentazole in two steps: reduction by an alkali metal to form the phenylpentazole radical anion, followed by thermal dissociation to yield cyclo-N5- . The reaction solution was analyzed by HPLC coupled with negative mode mass spectrometry. A signal with m/z 70 was eluted about 2.1 min after injection of the sample. Its identification as N5 was supported by single and double labeling with 15 N, which yielded signals at m/z=71 and 72, respectively, with identical retention times in the HPLC column. MS/MS analysis of the m/z=70 signal revealed a dissociation product with m/z=42, which can be assigned to N3- . To our knowledge this is the first preparation of cyclo-N5- in the bulk. The compound is indefinitely stable at temperatures below -40 °C, and has a half-life of a few minutes at room temperature.

4.
J Phys Chem A ; 114(39): 10563-74, 2010 Oct 07.
Article in English | MEDLINE | ID: mdl-20831205

ABSTRACT

The first excited state of BIDP was shown in a previous communication to exhibit an ultrafast decay in fluid nonpolar, nonprotic solutions due to the presence of a S(1)/S(0) conical intersection (CI). In frozen polar and nonpolar glasses a strong fluorescence was observed, rationalized by the hindering of the internal torsion required to reach the geometry of the CI. Complete analysis of the data was hampered by some unusual observations in nonpolar glasses. In this paper we show that they can be explained by assuming dimer formation, with a formation constant of K(eq) = (4 ± 3) × 10(5) M(-1) at 83 K and ΔH(dim) = 7 ± 2 kcal/mol. A complete analysis of the spectra is presented, and fluorescence quantum yields of the monomer and dimer are reported. Efficient self-quenching is found, with a Stern Volmer constant, K(SV) = (1.5 ± 0.1) × 10(6) M(-1), assigned to static quenching. The dimer absorption spectrum was extracted from the data and is compared to Kasha's exciton model and to quantum chemical (QC) calculations. The basic features of exciton splitting are reproduced by quantum mechanical calculations, but complete quantitative agreement of the QC computations with the experimental results is not attained. The previous analysis of the monomer spectra using the displaced harmonic oscillator model is extended to the more demanding conditions prevailing at cryogenic temperatures. The derived ΔH(dim) is in good agreement with other dimers formation enthalpies and with the quantum mechanical calculation presented. The new analysis corrects τ(f) in MCHIP to 2.9 × 10(-13) s, somewhat smaller than the value reported in polar solvent in a previous communication, thereby strengthening the assumption that polarity can reduce the efficiency of CI.


Subject(s)
Dihydropyridines/chemistry , Glass/chemistry , Indenes/chemistry , Dimerization , Molecular Dynamics Simulation , Molecular Structure , Photochemistry , Quantum Theory , Thermodynamics
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