scholarly journals Measurement of Electric Fields Experienced by Urea Guest Molecules in the 18-Crown-6/Urea (1:5) Host–Guest Complex: An Experimental Reference Point for Electric-Field-Assisted Catalysis

2019 ◽  
Vol 141 (9) ◽  
pp. 3965-3976 ◽  
Author(s):  
Ming W. Shi ◽  
Sajesh P. Thomas ◽  
Venkatesha R. Hathwar ◽  
Alison J. Edwards ◽  
Ross O. Piltz ◽  
...  
Keyword(s):  
Electric Field ◽  
Electric Fields ◽  
Reference Point ◽  
Guest Complex ◽  
Guest Molecules ◽  
Host Guest Complex ◽  
Experimental Reference

scholarly journals Supramolecular Stark Effect in Host-Guest Complexes via Charge Density Analysis

2014 ◽  
Vol 70 (a1) ◽  
pp. C674-C674
Author(s):  
Sajesh Thomas ◽  
Rebecca Fuller ◽  
Alexandre Sobolev ◽  
Philip Schauer ◽  
Simon Grabowsky ◽  
...  
Keyword(s):  
Electric Field ◽  
Charge Density ◽  
Electric Fields ◽  
Active Sites ◽  
Stark Effect ◽  
Dipole Moments ◽  
Covalent Bonds ◽  
Guest Molecules ◽  
Density Mapping ◽  
Density Analysis

The effect of an electric field on the vibrational spectra, the Vibrational Stark Effect (VSE), has been utilized extensively to probe the local electric field in the active sites of enzymes [1, 2]. For this reason, the electric field and consequent polarization effects induced by a supramolecular host system upon its guest molecules attain special interest due to the implications for various biological processes. Although the host-guest chemistry of crown ether complexes and clathrates is of fundamental importance in supramolecular chemistry, many of these multicomponent systems have yet to be explored in detail using modern techniques [3]. In this direction, the electrostatic features associated with the host-guest interactions in the inclusion complexes of halogenated acetonitriles and formamide with 18-crown-6 host molecules have been analyzed in terms of their experimental charge density distribution. The charge density models provide estimates of the molecular dipole moment enhancements which correlate with the simulated values of dipole moments under electric field. The accurate electron density mapping using the multipole formalism also enable the estimation of the electric field experienced by the guest molecules. The electric field vectors thus obtained were utilized to estimate the vibrational stark effect in the nitrile (-C≡N) and carbonyl (C=O) stretching frequencies of the guest molecules via quantum chemical calculations in gas phase. The results of these calculations indicate remarkable elongation of C≡N and C=O bonds due to the electric fields. The electronic polarization in these covalent bonds induced by the field manifests as notable red shifts in their characteristic vibrational frequencies. These results derived from the charge densities are further supported by FT-IR experiments and thus establish the significance of a phenomenon that could be termed as the "supramolecular Stark effect" in crystal environment.

Tuning the Electric Field Response of MOFs by Rotatable Dipolar Linkers

2019 ◽  
Author(s):  
Johannes P. Dürholt ◽  
Babak Farhadi Jahromi ◽  
Rochus Schmid
Keyword(s):  
Electric Field ◽  
Electric Fields ◽  
Structural Changes ◽  
Dielectric Behavior ◽  
Two Dimensions ◽  
Dielectric Constants ◽  
Electric Response ◽  
Dipole Strength ◽  
Metal Organic ◽  
Dynamics Simulations

Recently the possibility of using electric fields as a further stimulus to trigger structural changes in metal-organic frameworks (MOFs) has been investigated. In general, rotatable groups or other types of mechanical motion can be driven by electric fields. In this study we demonstrate how the electric response of MOFs can be tuned by adding rotatable dipolar linkers, generating a material that exhibits paralectric behavior in two dimensions and dielectric behavior in one dimension. The suitability of four different methods to compute the relative permittivity κ by means of molecular dynamics simulations was validated. The dependency of the permittivity on temperature T and dipole strength μ was determined. It was found that the herein investigated systems exhibit a high degree of tunability and substantially larger dielectric constants as expected for MOFs in general. The temperature dependency of κ obeys the Curie-Weiss law. In addition, the influence of dipolar linkers on the electric field induced breathing behavior was investigated. With increasing dipole moment, lower field strength are required to trigger the contraction. These investigations set the stage for an application of such systems as dielectric sensors, order-disorder ferroelectrics or any scenario where movable dipolar fragments respond to external electric fields.

scholarly journals Testing automatic methods to predict free binding energy of host–guest complexes in SAMPL7 challenge

2021 ◽  
Vol 35 (2) ◽  
pp. 209-222
Author(s):  
Dylan Serillon ◽  
Carles Bo ◽  
Xavier Barril
Keyword(s):  
Degrees Of Freedom ◽  
Binding Free Energy ◽  
Binding Mode ◽  
Specific System ◽  
New Host ◽  
Guest Molecules ◽  
Host Guest Complex ◽  
Automatic Methods ◽  
Material Sciences ◽  
Fundamental Direction

AbstractThe design of new host–guest complexes represents a fundamental challenge in supramolecular chemistry. At the same time, it opens new opportunities in material sciences or biotechnological applications. A computational tool capable of automatically predicting the binding free energy of any host–guest complex would be a great aid in the design of new host systems, or to identify new guest molecules for a given host. We aim to build such a platform and have used the SAMPL7 challenge to test several methods and design a specific computational pipeline. Predictions will be based on machine learning (when previous knowledge is available) or a physics-based method (otherwise). The formerly delivered predictions with an RMSE of 1.67 kcal/mol but will require further work to identify when a specific system is outside of the scope of the model. The latter is combines the semiempirical GFN2B functional, with docking, molecular mechanics, and molecular dynamics. Correct predictions (RMSE of 1.45 kcal/mol) are contingent on the identification of the correct binding mode, which can be very challenging for host–guest systems with a large number of degrees of freedom. Participation in the blind SAMPL7 challenge provided fundamental direction to the project. More advanced versions of the pipeline will be tested against future SAMPL challenges.

scholarly journals Meta-Deflectors Made of Dielectric Nanohole Arrays with Anti-Damage Potential

Photonics ◽  
2021 ◽  
Vol 8 (4) ◽  
pp. 107
Author(s):  
Haichao Yu ◽  
Feng Tang ◽  
Jingjun Wu ◽  
Zao Yi ◽  
Xin Ye ◽  
...  
Keyword(s):  
Electric Field ◽  
Electric Fields ◽  
Laser Cutting ◽  
High Complexity ◽  
Damage Potential ◽  
Optical Components ◽  
Nanohole Arrays ◽  
Intense Light ◽  
Polarization Of Light ◽  
Air Hole

In intense-light systems, the traditional discrete optical components lead to high complexity and high cost. Metasurfaces, which have received increasing attention due to the ability to locally manipulate the amplitude, phase, and polarization of light, are promising for addressing this issue. In the study, a metasurface-based reflective deflector is investigated which is composed of silicon nanohole arrays that confine the strongest electric field in the air zone. Subsequently, the in-air electric field does not interact with the silicon material directly, attenuating the optothermal effect that causes laser damage. The highest reflectance of nanoholes can be above 99% while the strongest electric fields are tuned into the air zone. One presentative deflector is designed based on these nanoholes with in-air-hole field confinement and anti-damage potential. The 1st order of the meta-deflector has the highest reflectance of 55.74%, and the reflectance sum of all the orders of the meta-deflector is 92.38%. The optothermal simulations show that the meta-deflector can theoretically handle a maximum laser density of 0.24 W/µm2. The study provides an approach to improving the anti-damage property of the reflective phase-control metasurfaces for intense-light systems, which can be exploited in many applications, such as laser scalpels, laser cutting devices, etc.

scholarly journals Integrating flexible electronics for pulsed electric field delivery in a vascularized 3D glioblastoma model

2021 ◽  
Vol 5 (1) ◽  
Author(s):  
Marie C. Lefevre ◽  
Gerwin Dijk ◽  
Attila Kaszas ◽  
Martin Baca ◽  
David Moreau ◽  
...  
Keyword(s):  
Electric Field ◽  
Electric Fields ◽  
Flexible Electronics ◽  
Soft Tissues ◽  
Multiphoton Microscopy ◽  
Membrane Integrity ◽  
Tumor Model ◽  
Pulsed Electric Fields ◽  
In Ovo ◽  
Cell Membrane Integrity

AbstractGlioblastoma is a highly aggressive brain tumor, very invasive and thus difficult to eradicate with standard oncology therapies. Bioelectric treatments based on pulsed electric fields have proven to be a successful method to treat cancerous tissues. However, they rely on stiff electrodes, which cause acute and chronic injuries, especially in soft tissues like the brain. Here we demonstrate the feasibility of delivering pulsed electric fields with flexible electronics using an in ovo vascularized tumor model. We show with fluorescence widefield and multiphoton microscopy that pulsed electric fields induce vasoconstriction of blood vessels and evoke calcium signals in vascularized glioblastoma spheroids stably expressing a genetically encoded fluorescence reporter. Simulations of the electric field delivery are compared with the measured influence of electric field effects on cell membrane integrity in exposed tumor cells. Our results confirm the feasibility of flexible electronics as a means of delivering intense pulsed electric fields to tumors in an intravital 3D vascularized model of human glioblastoma.

scholarly journals Electro-Optic Control of Lithium Niobate Bulk Whispering Gallery Resonators: Analysis of the Distribution of Externally Applied Electric Fields

Crystals ◽  
2021 ◽  
Vol 11 (3) ◽  
pp. 298
Author(s):  
Yannick Minet ◽  
Hans Zappe ◽  
Ingo Breunig ◽  
Karsten Buse
Keyword(s):  
Lithium Niobate ◽  
Electric Field ◽  
Electric Fields ◽  
Frequency Comb ◽  
Parametric Oscillation ◽  
Pockels Effect ◽  
Optical Mode ◽  
Cylindrical Resonator ◽  
Whispering Gallery ◽  
Electro Optic

Whispering gallery resonators made out of lithium niobate allow for optical parametric oscillation and frequency comb generation employing the outstanding second-order nonlinear-optical properties of this material. An important knob to tune and control these processes is, e.g., the linear electro-optic effect, the Pockels effect via externally applied electric fields. Due to the shape of the resonators a precise prediction of the electric field strength that affects the optical mode is non-trivial. Here, we study the average strength of the electric field in z-direction in the region of the optical mode for different configurations and geometries of lithium niobate whispering gallery resonators with the help of the finite element method. We find that in some configurations almost 100% is present in the cavity compared to the ideal case of a cylindrical resonator. Even in the case of a few-mode resonator with a very thin rim we find a strength of 90%. Our results give useful design considerations for future arrangements that may benefit from the strong electro-optic effect in bulk whispering gallery resonators made out of lithium niobate.

Illustration of a computational pipeline for evaluating cyclodextrin host–guest complex formation through conformational capture of bullvalene

2021 ◽  
Vol 154 (15) ◽  
pp. 154105
Author(s):  
Zahra Shadfar ◽  
Oussama Yahiaoui ◽  
Thomas A. Collier ◽  
Thomas Fallon ◽  
Jane R. Allison
Keyword(s):  
Complex Formation ◽  
Computational Pipeline ◽  
Guest Complex ◽  
Host Guest Complex

scholarly journals Double layers in the downward current region of the aurora

2003 ◽  
Vol 10 (1/2) ◽  
pp. 45-52 ◽  
Author(s):  
R. E. Ergun ◽  
L. Andersson ◽  
C. W. Carlson ◽  
D. L. Newman ◽  
M. V. Goldman
Keyword(s):  
Magnetic Field ◽  
Electron Beam ◽  
Phase Space ◽  
Electric Field ◽  
Electric Fields ◽  
Double Layers ◽  
Parallel Electric Field ◽  
Electrostatic Waves ◽  
Current Region ◽  
Decisive Evidence

Abstract. Direct observations of magnetic-field-aligned (parallel) electric fields in the downward current region of the aurora provide decisive evidence of naturally occurring double layers. We report measurements of parallel electric fields, electron fluxes and ion fluxes related to double layers that are responsible for particle acceleration. The observations suggest that parallel electric fields organize into a structure of three distinct, narrowly-confined regions along the magnetic field (B). In the "ramp" region, the measured parallel electric field forms a nearly-monotonic potential ramp that is localized to ~ 10 Debye lengths along B. The ramp is moving parallel to B at the ion acoustic speed (vs) and in the same direction as the accelerated electrons. On the high-potential side of the ramp, in the "beam" region, an unstable electron beam is seen for roughly another 10 Debye lengths along B. The electron beam is rapidly stabilized by intense electrostatic waves and nonlinear structures interpreted as electron phase-space holes. The "wave" region is physically separated from the ramp by the beam region. Numerical simulations reproduce a similar ramp structure, beam region, electrostatic turbulence region and plasma characteristics as seen in the observations. These results suggest that large double layers can account for the parallel electric field in the downward current region and that intense electrostatic turbulence rapidly stabilizes the accelerated electron distributions. These results also demonstrate that parallel electric fields are directly associated with the generation of large-amplitude electron phase-space holes and plasma waves.

scholarly journals Clarifications on the Behavior of Alternative Gases to SF6 in Divergent Electric Field Distributions under AC Voltage

Energies ◽  
2021 ◽  
Vol 14 (4) ◽  
pp. 1065
Author(s):  
Houssem Eddine Nechmi ◽  
Michail Michelarakis ◽  
Abderrahmane (Manu) Haddad ◽  
Gordon Wilson
Keyword(s):  
Electric Field ◽  
Electric Fields ◽  
Partial Discharge ◽  
Mean Value ◽  
Electrode System ◽  
Polarity Reversal ◽  
Buffer Gas ◽  
Co2 Gas ◽  
Breakdown Mechanism ◽  
Positive Cycle

Negative and positive partial discharge inception voltages and breakdown measurements are reported in a needle-plane electrode system as a function of pressure under AC voltage for natural gases (N2, CO2, and O2/CO2), pure NovecTM gases (C4F7N and C5F10O) and NovecTM in different natural gas admixtures. For compressed 4% C4F7N–96% CO2 and 6% C5F10O–12% O2–82% CO2 gas mixtures, the positive-streamer mode is identified as the breakdown mechanism. Breakdown and negative partial discharge inception voltages of 6% C5F10O–12% O2–82% CO2 are higher than those of 4% C4F7N–96% CO2. At 8.8 bar abs, the breakdown voltage of 6% C5F10O–12% O2–82% CO2 is equal to that of 12.77% O2–87.23% CO2 (buffer gas). Synergism in negative partial discharge inception voltage/electric field fits with the mean value and the sum of each partial pressure individually component for a 20% C4F7N–80% CO2 and 6% C5F10O–12% O2–82% CO2, respectively. In 9% C4F7N–91% CO2, the comparison of partial discharge inception electric fields is Emax (CO2) = Emax(C4F7N), and Emax (12.77% O2–87.23% CO2) = Emax(C5F10O) in 19% C5F10O–81%(12.77% O2–87.23% CO2). Polarity reversal occurs under AC voltage when the breakdown polarity changes from negative to positive cycle. Polarity reversal electric field EPR was quantified. Fitting results show that EPR (CO2) = EPR(9% C4F7N–91% CO2) and EPR(SF6) = EPR (22% C4F7N–78% CO2). EPR (4% C4F7N–96% CO2) = EPR (12.77% O2–87.23% CO2) and EPR (6% C5F10O–12% O2–82% CO2) < EPR (4% C4F7N–96% CO2) < EPR (CO2).

scholarly journals Tuning Single-Molecule Conductance by Controlled Electric Field-Induced trans-to-cis Isomerisation

2021 ◽  
Vol 11 (8) ◽  
pp. 3317
Author(s):  
C.S. Quintans ◽  
Denis Andrienko ◽  
Katrin F. Domke ◽  
Daniel Aravena ◽  
Sangho Koo ◽  
...  
Keyword(s):  
Electric Field ◽  
Electric Fields ◽  
Single Molecule ◽  
Quantum Interference ◽  
Single Molecule Level ◽  
Wet Chemical Synthesis ◽  
Single Molecule Junctions ◽  
Tunnelling Microscopy ◽  
The Difference

External electric fields (EEFs) have proven to be very efficient in catalysing chemical reactions, even those inaccessible via wet-chemical synthesis. At the single-molecule level, oriented EEFs have been successfully used to promote in situ single-molecule reactions in the absence of chemical catalysts. Here, we elucidate the effect of an EEFs on the structure and conductance of a molecular junction. Employing scanning tunnelling microscopy break junction (STM-BJ) experiments, we form and electrically characterize single-molecule junctions of two tetramethyl carotene isomers. Two discrete conductance signatures show up more prominently at low and high applied voltages which are univocally ascribed to the trans and cis isomers of the carotenoid, respectively. The difference in conductance between both cis-/trans- isomers is in concordance with previous predictions considering π-quantum interference due to the presence of a single gauche defect in the trans isomer. Electronic structure calculations suggest that the electric field polarizes the molecule and mixes the excited states. The mixed states have a (spectroscopically) allowed transition and, therefore, can both promote the cis-isomerization of the molecule and participate in electron transport. Our work opens new routes for the in situ control of isomerisation reactions in single-molecule contacts.

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