Changes In Electrostatic Potential Research Articles

Microscopic mechanism of oxygen consumption inhibitor delaying the oxidation of coal

In order to inhibit the coal-oxygen complex that triggers spontaneous coal combustion, a retardant consisting of sodium alginate solution, sodium bicarbonate, inorganic salt MgCl2 and deoxidiser that can achieve multiple effects of hysteresis and oxygen depletion was developed. Taking the sulfur-containing side-chain reactive group of coal molecule -CH2-SH as the object of study, the Gaussian 16W procedure and density-functional-transfer theory (DFT) were applied to investigate the electrostatic potential and reaction tendency, oxygen adsorption capacity, front-line orbitals, natural bonding capacity, and oxygen adsorption capacity of the reactive group before and after the formation of the complexes with Na+ and Mg2+, using the solvation effect at the level of B3LYP/6-31G(d, p), respectively. The changes of electrostatic potential and reaction tendency, oxygen adsorption, front orbitals, natural bonding orbitals and charge transfer before and after the formation of complexes between -CH2-SH reactive groups and Na+, Mg2+, respectively. Comparative analysis of the interaction with oxygen before and after the formation of coordination blocking structure of coal and inorganic salts in gaseous environment, aqueous environment and retarded oxygen-depleting sodium alginate blocking solution environment, respectively. The calculated results show that the side chain of the aromatic ring of the raw coal is the active site for easy adsorption of oxygen, and the stability of the coordination blocking structure is significantly enhanced under the environment of hysteretic oxygen-depleting sodium alginate gel blocking agent, and the adsorption of oxygen before and after the coal molecule combines with Na+ and Mg2+ is the weakest under the environment of hysteretic oxygen-depleting sodium alginate gel blocking agent; The absolute value of the HOMO orbital energy increases the most, and the energy level difference (ELUMO - EHOMO) of the complexes increases the most; the natural bonding orbital analysis reveals that the lone pair of electrons of S atoms in -CH2-SH under the environment of hysteresis oxygen depletion sodium alginate gel blocker has a strong coordination effect with Na+ and Mg2+. In the hysteresis oxygen depletion sodium alginate gel resist environment, the stability of the coordination blocking structure is strengthened due to the moderateness of the dielectric constant, and its oxygen depletion also reduces the number of O2 molecules, which further reduces the adsorption and collision chances between the two, and a more desirable blocking effect can be obtained. The results reveal the micro-mechanism of the hysteresis oxygen depletion inhibitor in preventing spontaneous combustion of coal, which can provide a reference for further improving the inhibition effect of the inhibitor.

Investigation of AlGaN UV emitting tunnel junction LED devices by off-axis electron holography

Here we use off-axis electron holography combined with advanced transmission electron microscopy techniques to understand the opto-electronic properties of AlGaN tunnel junction (TJ)-light-emitting diode (LED) devices for ultraviolet emission. Four identical AlGaN LED devices emitting at 290 nm have been grown by metal–organic chemical vapour deposition. Then Ge doped n-type regions with and without InGaN or GaN interlayers (IL) have been grown by molecular beam epitaxy onto the top Mg doped p-type layer to form a TJ and hence a high quality ohmic metal contact. Off-axis electron holography has then been used to demonstrate a reduction in the width of the TJ from 9.5 to 4.1 nm when an InGaN IL is used. As such we demonstrate that off-axis electron holography can be used to reproducibly measure nm-scale changes in electrostatic potential in highly defected and challenging materials such as AlGaN and that systematic studies of devices can be performed. The LED devices are then characterized using standard opto-electric techniques and the improvements in the performance of the LEDs are correlated with the electron holography results.

Redox Properties of Flavin in BLUF and LOV Photoreceptor Proteins from Hybrid QM/MM Molecular Dynamics Simulation.

Flavins play an important role in many oxidation and reduction processes in biological systems. For example, flavin adenine dinucleotide (FAD) and flavin mononucleotide (FMN) are common cofactors found in enzymatic proteins that use the special redox properties of these flavin molecules for their catalytic or photoactive functions. The redox potential of the flavin is strongly affected by its (protein) environment; however, the underlying molecular interactions of this effect are still unknown. Using hybrid quantum mechanics/molecular mechanics (QM/MM) simulation techniques, we have studied the redox properties of flavin in the gas phase, aqueous solution, and two different protein environments, in particular, a BLUF and a LOV photoreceptor domain. By mapping the changes in electrostatic potential and solvent structure, we gain insight into how specific polarization of the flavin by its environment tunes the reduction potential. We find also that accurate calculation of the reduction potentials of these systems by using the hybrid QM/MM approach is hampered by a too limited sampling of the counterion configurations and by artifacts at the QM/MM boundary. We make suggestions for how these issues can be overcome.

Effect of a single methyl substituent on the electronic structure of cobaltocene studied by computationally assisted MATI spectroscopy.

Metallocenes represent archetypical organometallic compounds playing key roles in various fields of fundamental and applied chemistry. Many of their unique properties arise from low ionization energies (IE) which can be tuned by introducing substituents into the rings. Here we report the first mass-analyzed threshold ionization (MATI) spectrum of a methylmetallocene, (Cp')(Cp)Co (Cp' = η5-C5H4Me, Cp = η5-C5H5). The presence of a single Me group allows us to study the "pure" effect of methylation without the mutual influence of substituents. The MATI technique provides an extremely high accuracy in determining the adiabatic IE of (Cp')(Cp)Co which equals 5.2097(6) eV. The effect of a Me group on the IE of cobaltocene appears to be 36% stronger than that in bis(η6-benzene)chromium. The MATI spectrum of (Cp')(Cp)Co shows a rich vibronic structure from which vibrational frequencies of the free ion are determined. This information provides a solid basis for testing the quality of quantum chemical calculations. Various levels of the DFT and coupled cluster computations are used to describe the structural and electronic transformations accompanying the detachment of an elctron from (Cp')(Cp)Co. New aspects of the methyl substituent influence on the potential energy surfaces, as well as on the inhomogeneous changes in charge density and electrostatic potential caused by ionization, are discussed.

(Invited) Predicting the Response of Carbon Nanotube Field-Effect Biosensors Using Simulations

Objectives Carbon nanotube field-effect biosensors (bioCNTFETs) are a promising platform to detect biomolecular analytes because they are highly sensitive, specific, low-cost, portable, and integrable into arrays for multiplexed sensing [1]. Their sensitivity originates from carbon nanotubes having electrical properties that are strongly dependent on nearby biomolecules. As a result, the biosensor detects an electrical current through the network of nanotubes that depends on the concentration of analyte. To achieve specificity, carbon nanotubes need to be functionalized with a probe molecule that binds to a specific target analyte. However, it has been demonstrated that the response of bioCNTFETs strongly depends on the attachment site on the probe molecule to the carbon nanotube [2], and this variability is impairing the development of bioCNTFETs.To address this challenge, we are developing an integrated approach combining simulation and experiment: simulations are used to predict which attachment sites on the binding protein are expected to generate the greatest response, then devices are fabricated using phenyl azide photochemistry to precisely attach the binding protein via these sites on the nanotubes. To validate our approach, we characterized a bioCNTFET covalently functionalized with the beta-lactamase inhibitor protein II (BLIP-II) to detect beta-lactamases such as TEM-1 and KPC-2 that are associated with antimicrobial resistance. Results Our simulation protocol is based on molecular dynamics to sample the biomolecule-nanotube interactions and then on Poisson-Boltzmann calculations to estimate the electrostatic potential generated on the nanotube’s surface by the conformations of the biomolecule [3]. Since electrostatic potential changes on the surface of the nanotubes in the BLIP-II biosensor are expected to cause the electrical signal changes detected, we specifically quantify that as TEM-1 or KPC-2 binds to the covalently attached BLIP-II to the nanotube. We looked at two different attachment sites on BLIP-II – A41 and T213 – that are expected to produce a different response. For the A41 site, we show that the electrostatic potential doesn’t change significantly as TEM-1 or KPC-2 binds to BLIP-II because they are too far from the nanotube. However, the T213 site allows significant electrostatic potential changes: TEM-1 shifts the potential to more negative values, while KPC-2 shifts the potential to less negative values.The predictions from our simulations agree with measurements done on devices. For the A41 site, the measured conductance doesn’t change significantly upon binding of TEM-1 or KPC-2, indicating that the electrostatic potential on the nanotube doesn’t change much, as predicted. For the T213 site, the measured conductance increases significantly upon binding of TEM-1, while it decreases significantly for KPC-2. This suggests more p-type carriers in the nanotube (due to a more negative potential on the nanotube) as TEM-1 binds, but less p-type carriers (due to a less negative potential) as KPC-2 binds, as predicted. Conclusions We have developed a simulation protocol that predicts, in agreement with experimental measurements, the impact of the probe’s attachment site on the conductance modulation detected by carbon-nanotube field-effect biosensors. This supports the development of a truly integrated approach combining simulation and experiment to consistently design and fabricate these biosensors to achieve optimized sensitivity.

Near-Infrared CMOS Image Sensors Enabled by Colloidal Quantum Dot-Silicon Heterojunction

The solution processibility of colloidal quantum dots (CQDs) promises a straightforward integration with Si readout integrated circuits (Si-ROCIs), which enables a near-infrared (NIR) CMOS image sensor (CIS; CMOS stands for complementary metal-oxide semiconductor). Previously demonstrated CQD NIR CISs were achieved through integrating CQD photodiode or PhotoFET with Si-ROCIs. Here, we conduct a simulation study to investigate the feasibility of a NIR CIS enabled by another integration strategy, that is, by forming a CQD-Si heterojunction. Simulation results clearly show that each active pixel made of CQD-Si heterojunction photodiode on the CIS sensitively responds to NIR light, and generated photocarriers induce changes in electrostatic potentials in the active pixel. The potential changes are read out through the integrated circuits as validated by the readout timing sequence simulation.

Mapping of the Electrostatic Potentials in a Fully Processed Led Device with nm-Scale Resolution by In Situ off-Axis Electron Holography.

The optoelectronic properties of a fully processed red emitting AlGaInP micro-diode device is measured using standard I-V and luminescence measurements. A thin specimen is then prepared for in situ transmission electron microscopy analysis by focused ion beam milling, then the changes of electrostatic potential as a function of applied forward bias voltage are mapped by off-axis electron holography. We demonstrate that the quantum wells in the diode sit on a potential gradient until the threshold forward bias voltage for light emission is reached; at which point the quantum wells are aligned at the same potential. From simulations, a similar effect for the band structure can be demonstrated, where the quantum wells are aligned at the same energy level, and contain electrons and holes that are available for radiative recombination at this threshold voltage. We demonstrate that off-axis electron holography can be used to directly measure the potential distribution in optoelectronic devices, and is a powerful tool to help better understand their performance and to improve simulations.

Phosphorus-Enhanced and Calcium-Retarded Transport of Ferrihydrite Colloid: Mechanism of Electrostatic Potential Changes Regulated via Adsorption Speciation.

The transport of ferrihydrite colloid (FHC) through porous media is influenced by anions (e.g., PO43-) and cations (e.g., Ca2+) in the aqueous environment. This study investigated the cotransport of FHC with P and P/Ca in saturated sand columns. The results showed that P adsorption enhanced FHC transport, whereas Ca loaded onto P-FHC retarded FHC transport. Phosphate adsorption provided a negative potential on the FHC, while Ca added to P-FHC led to electrostatic screening, compression of the electric double layer, and formation of Ca5(PO4)3OH followed by heteroaggregation at pH ≥ 6.0. The monodentate and bidentate P surface complexes coexisted, and Ca mainly formed a ternary complex with bidentate P (≡(FeO)2PO2Ca). The unprotonation bidentate P at the Stern 1-plane had a considerable negative potential at the Van der Waals molecular surface. Extending the potential effect to the outer layer of FHC, the potential at the Stern 2-plane and zeta potential exhibited a corresponding change, resulting in a change in FHC mobility, which was validated by comparison of experimental results, DFT calculations, and CD-MUSIC models. Our results highlighted the influence of P and Ca on FHC transport and elucidated their interaction mechanisms based on quantum chemistry and colloidal chemical interface reactions.

Effect of Structural Targeted Modifications on the Potential Allergenicity of Peanut Allergen Ara h 2

Protein structure affects allergenicity, and critical structural elements, especially conformational epitopes that determine allergenicity, have attracted a great deal of interest. In this study, we aimed to identify the localized structure that affects the potential allergenicity of protein by making targeted modifications of Ara h 2 and comparing the structure and allergenicity of mutants with those of the wide-type allergen. The structures of the allergen and its mutants were characterized by circular dichroism and ultraviolet absorption spectroscopy and simulated by molecular dynamics. The allergenicity was assessed by Western blotting, an indirect competitive enzyme-linked immunosorbent assay, a cell model, and a mouse model. Then, the structures that affect allergenicity were analyzed and screened. Our results showed that mutations in amino acids changed the nearby localized structure and the overall structures. The structural changes affected the IgE binding capacity of the allergen and reduced its potential allergenicity. The solvent accessible surface area (SASA) of aromatic residues was positively correlated with the IgE binding capacity. The integrity of the disulfide bond is also critical for the binding of IgE to allergens. Interestingly, different mutations induced similar electrostatic potential and allergenicity changes, such as localized structure R62DPYSPSQDPYSPS75. In conclusion, the disulfide bond and the SASA of aromatic residues are important for the allergenicity of Ara h 2. The localized structure R62DPYSPSQDPYSPS75 is also crucial for the allergenicity of Ara h 2.

N/S co-doped microporous zeolite-templated carbon for efficient CO2 adsorption and separation

Heteroatomic doping of porous carbon materials can give rise to variations in the electronic structure and properties, and has been used to enhance the adsorption and separation of CO2. Herein, N and S doped zeolite-templated carbon (ZTC) are synthesized to study their CO2 adsorption and selective from CO2/N2. ZTC-N, ZTC-S and ZTC-NS exhibit comparatively high CO2 adsorption of 6.12, 7.73 and 9.32 mmol g−1 at 0 °C, which are more than three times than that of ZTC (1.98 mmol g−1). The CO2 adsorption capacity for ZTC-NS at 25 °C and 1 bar can reach as high as 6.03 mmol g−1, which can still occupy approximately 96% after 5 cycles. The obtained carbon materials ZTC-NS with the smallest BET surface area show the highest CO2 adsorption capacity, which indicate an obvious synergistic enhancement effect between sulfur and nitrogen doping. The detailed theoretical calculations indicate N and S co-doping into porous carbon materials assists the change of electrostatic surface potential and local electronic density, thus enhanced the CO2 adsorption.

Computational investigation of the conformer selective complexes of 1,2,3,4-tetrahydroisoquinoline: Ammonia (THIQ: NH3) in S0

Three low-energy conformations are identified in 1,2,3,4-tetrahydroisoquinoline (THIQ): NH3 complexes. The lone pairs on N atoms strongly affects the conformational landscape. Both density functional theory (DFT) and MP2 levels of computations yield consistent results. Multiple PESs corresponding to different types of hydrogen bonds are drawn to account for all possible complexes. Ten complexes are identified. The global minimum contains a strong N-H⋅⋅⋅N and a weak N-H⋅⋅⋅π hydrogen bonds where NH3 is an H bond acceptor. In the remaining two complexes ammonia acts as a donor. All the low-energy complexes which can show intermolecular proton transfer were studied in detail although none shows PT with a single NH3 molecule. The intermolecular vibrational modes are critically analyzed and the relative shifts in the characteristic modes of ammonia are explained. Types and sites for H-bonding can be ascertained from the vibrational analyses. Changes in molecular electrostatic potentials (MEP) on complex formation are explained and confirm our computational results. We suggest further experiments to confirm our key observations.

Tuning Electrostatic and Hydrophobic Surfaces of Aromatic Rings to Enhance Membrane Association and Cell Uptake of Peptides

AbstractAromatic groups are key mediators of protein–membrane association at cell surfaces, contributing to hydrophobic effects and π‐membrane interactions. Here we show electrostatic and hydrophobic influences of aromatic ring substituents on membrane affinity and cell uptake of helical, cyclic and cell penetrating peptides. Hydrophobicity is important, but subtle changes in electrostatic surface potential, dipoles and polarizability also enhance association with phospholipid membranes and cell uptake. A combination of fluorine and sulfur substituents on an aromatic ring induces microdipoles that enhance cell uptake of 12‐residue peptide inhibitors of p53‐HDM2 interaction and of cell‐penetrating cyclic peptides. These aromatic motifs can be readily inserted into peptide sidechains to enhance their cell uptake.

Tuning Electrostatic and Hydrophobic Surfaces of Aromatic Rings to Enhance Membrane Association and Cell Uptake of Peptides.

Aromatic groups are key mediators of protein–membrane association at cell surfaces, contributing to hydrophobic effects and π‐membrane interactions. Here we show electrostatic and hydrophobic influences of aromatic ring substituents on membrane affinity and cell uptake of helical, cyclic and cell penetrating peptides. Hydrophobicity is important, but subtle changes in electrostatic surface potential, dipoles and polarizability also enhance association with phospholipid membranes and cell uptake. A combination of fluorine and sulfur substituents on an aromatic ring induces microdipoles that enhance cell uptake of 12‐residue peptide inhibitors of p53‐HDM2 interaction and of cell‐penetrating cyclic peptides. These aromatic motifs can be readily inserted into peptide sidechains to enhance their cell uptake.

Effects of the Temperature and Salt Concentration on the Structural Characteristics of the Protein (PDB Code 1BBL).

The effect of the temperature and salt solution on the structural characteristics of the protein 1BBL was investigated by molecular dynamics simulations. The paper presents simulation results regarding the non-bonded energy and the structural stability of the protein immersed in salt solutions with different concentrations and temperatures. Our work demonstrates that the electrostatic potential energy and van der Waals energy of the system show the opposite changes with the influence of the external environment. Since the electrostatic potential energy changes more obviously, it is dominated in the non-bonding interactions. The structural parameters, such as the root mean square deviation and the radius of gyration, increased initially and decreased afterward with the increase of the salt concentration. The protein presented the loose structure with a relative low stability when it was immersed in a monovalent solution with a salt concentration of 0.8 mol/L. The salt concentration corresponding to the maximum value of structural parameters in the monovalent salt solution was double that in the divalent salt solution. It was also concluded that the protein presented a compact and stable structure when immersed in salt solutions with a high concentration of 2.3 mol/L. The analysis of the root mean square deviation and root mean square fluctuation of the protein sample also exhibited that the structural stability and chain flexibility are strongly guided by the effect of the temperature. These conclusions help us to understand the structural characteristics of the protein immersed in the salt solutions with different concentrations and temperatures.

Detecting Individual Proteins and Their Surface Charge Variations in Solution by the Potentiometric Nanoimpact Method.

Label-free detection and analysis of proteins in their natural form and their dynamic interactions with substrates at the single-molecule level are important for both fundamental studies and various applications. Herein, we demonstrate a simple potentiometric method to achieve this goal by detecting the native charge of protein in solution by utilizing the principle of single-entity electrochemistry techniques. When a charged protein moves near the vicinity of a floating carbon nanoelectrode connected to a high-impedance voltage meter, the distinct local electrostatic potential changes induced by the transient collision event of protein, also called the "nanoimpact" event, can be captured by the nanoelectrode as a potential probe. This potentiometric method is highly sensitive for charged proteins, and low-molecular-weight proteins less than 10 kDa can be detected in low-salt-concentration electrolytes. By analyzing the shape and magnitude of the recorded time-resolved potential change and its time derivative, we can reveal the charge and motion of the protein in the nonspecific protein-surface interaction event. The charge polarity variations of the proteins at different pH values were also successfully probed. Compared with synthetic spherical nanoparticles, the statistical analysis of many single-molecule nanoimpact events revealed a large variation in the recorded transient potential signals, which may be attributed to the intrinsic protein dynamics and surface charge heterogeneity, as suggested by the finite element method and molecular dynamic simulations.

Association Study of the M132L Single Nucleotide Polymorphism With Susceptibility to Chronic Wasting Disease in Korean Elk: A Meta-Analysis.

Chronic wasting disease (CWD) is a deleterious brain proteinopathy caused by a pathogenic form of prion protein (PrPSc), which is converted from a benign form of prion protein (PrPC) encoded by the prion protein gene (PRNP). In elk, the M132L single nucleotide polymorphism (SNP) of the PRNP gene likely plays a pivotal role in susceptibility to CWD. However, the association of the M132L SNP with susceptibility to CWD has not been evaluated in Korean elk to date. To estimate the association of the M132L SNP with susceptibility to CWD in Korean elk, we investigated the genotype and allele frequencies of the M132L SNP by amplicon sequencing and performed association analysis between CWD-positive and CWD-negative elk. In addition, we performed a meta-analysis to evaluate the association between the M132L SNP and susceptibility to CWD in quantitatively synthesized elk populations. Furthermore, we estimated the effect of the M132L SNP on elk PrP using in silico programs, including PolyPhen-2, PROVEAN, AMYCO and Swiss-PdbViewer. We did not identify a significant association between the M132L SNP of PRNP and susceptibility to CWD in Korean elk. The meta-analysis also did not identify a strong association between the M132L SNP of PRNP and susceptibility to CWD in quantitatively synthesized elk populations. Furthermore, we did not observe significant changes in structure, amyloid propensity or electrostatic potential based on the M132L SNP in elk PrP. To the best of our knowledge, this was the first report of an association analysis and meta-analysis in Korean elk and quantitatively synthesized elk populations, respectively.

Competitive Adsorption Processes at Clay Mineral Surfaces: A Coupled Experimental and Modeling Approach

Quantification of adsorption processes on clay mineral surfaces is often necessary to predict the extent and the evolution of contaminants’ migration in surficial and underground environments. Many studies have been dedicated to retention measurement as a function of pH and ionic strength in relation with the two main identified adsorption processes for clay minerals, that is, cation exchange on their basal surfaces and surface complexation on their edge surfaces. The latest process has been repeatedly assessed as an effective retention mechanism at circumneutral pH conditions, which often prevail in natural environments. This assessment must however be tempered by the lack of information about competitive processes that can take place with the numerous chemical species present in natural settings, compared to simplified systems investigated in laboratory experiments. In this study, we quantified experimentally the competition between Pb2+, Co2+, Zn2+, and Mg2+ for specific adsorption on montmorillonite edge surfaces. Zn2+ was an effective competitor with Pb2+ and Co2+, and our results showed also unambiguously the influence of Mg2+ concentration levels on the specific adsorption of Pb2+ and Co2+. Because of the high ionic strength used in the experiments, cation exchange with Mg2+ was dismissed as a possible reason for such competition process, leaving specific competitive adsorption on edge surfaces as a unique explanation for our observations. Modeling of Pb2+ adsorption data with a state-of-art electrostatic complexation model for montmorillonite edge surfaces, supported by state-of-the-art, made it possible to distinguish two types of possible competition driving forces: Zn2+ competition for adsorption site occupancy but also detrimental changes in surface electrostatic potential following Mg2+ adsorption on sites neighboring those of Pb2+ adsorption. Mg2+ competition observed in our experiment should apply in most of clayey environments. Consequently, adsorption data obtained on pure clay mineral phases, and the associated models that have been built based on these data without considering the geochemical background in competitive species, may overestimate the retention properties of clay minerals when applied to natural settings.

SARS-CoV-2 B.1.617 Indian variants: Are electrostatic potential changes responsible for a higher transmission rate?

Lineage B.1.617+, also known as G/452R.V3 and now denoted by WHO with the Greek letters δ and κ, is a recently described SARS‐CoV‐2 variant under investigation first identified in October 2020 in India. As of May 2021, three sublineages labeled as B.1.617.1 (κ), B.1.617.2 (δ), and B.1.617.3 have been already identified, and their potential impact on the current pandemic is being studied. This variant has 13 amino acid changes, three in its spike protein, which are currently of particular concern: E484Q, L452R, and P681R. Here, we report a major effect of the mutations characterizing this lineage, represented by a marked alteration of the surface electrostatic potential (EP) of the receptor‐binding domain (RBD) of the spike protein. Enhanced RBD‐EP is particularly noticeable in the B.1.617.2 (δ) sublineage, which shows multiple replacements of neutral or negatively charged amino acids with positively charged amino acids. We here hypothesize that this EP change can favor the interaction between the B.1.617+ RBD and the negatively charged ACE2, thus conferring a potential increase in the virus transmission.

Avoiding the Center-Symmetry Trap: Programmed Assembly of Dipolar Precursors into Porous, Crystalline Molecular Thin Films.

Liquid-phase, quasi-epitaxial growth is used to stack asymmetric, dipolar organic compounds on inorganic substrates, permitting porous, crystalline molecular materials that lack inversion symmetry. This allows material fabrication with built-in electric fields. A new programmed assembly strategy based on metal-organic frameworks (MOFs) is described that facilitates crystalline, noncentrosymmetric space groups for achiral compounds. Electric fields are integrated into crystalline, porous thin films with an orientation normal to the substrate. Changes in electrostatic potential are detected via core-level shifts of marker atoms on the MOF thin films and agree with theoretical results. The integration of built-in electric fields into organic, crystalline, and porous materials creates possibilities for band structure engineering to control the alignment of electronic levels in organic molecules. Built-in electric fields may also be used to tune the transfer of charges from donors loaded via programmed assembly into MOF pores. Applications include organic electronics, photonics, and nonlinear optics, since the absence of inversion symmetry results in a clear second-harmonic generation signal.

A β-Hairpin Motif in the Envelope Protein E2 Mediates Receptor Binding of Bovine Viral Diarrhea Virus.

Pestivirus envelope protein E2 is crucial to virus infection and accomplishes virus-receptor interaction during entry. However, mapping of E2 residues mediating these interactions has remained unexplored. In this study, to investigate the structure-function relationship for a β-hairpin motif exposed to the solvent in the crystal structure of bovine viral diarrhea virus (BVDV) E2, we designed two amino acidic substitutions that result in a change of electrostatic potential. First, using wild type and mutant E2 expressed as soluble recombinant proteins, we found that the mutant protein had reduced binding to susceptible cells compared to wild type and diminished ability to inhibit BVDV infection, suggesting a lower affinity for BVDV receptors. We then analyzed the effect of β-hairpin mutations in the context of recombinant viral particles. Mutant viruses recovered from cell culture supernatant after transfection of recombinant RNA had almost completely inhibited ability to re-infect susceptible cells, indicating an impact of mutations on BVDV infectivity. Finally, sequential passaging of the mutant virus resulted in the selection of a viral population in which β-hairpin mutations reverted to the wild type sequence to restore infectivity. Taken together, our results show that this conserved region of the E2 protein is critical for the interaction with host cell receptors.