Single Positive Charge Research Articles

Unveiling the impact of Fe-doping concentration on the local structure and morphological evolution of Cr2O3 nanoparticles

A series of Cr2−xFexO3 (0.0 ≤ x ≤ 0.3) nanoparticles were successfully synthesized using a sol-gel-based method. Analysis through XRD and SAED of both pure and Fe-doped Cr2O3 nanoparticles revealed a rhombohedral structure belonging to the R3‾cD3d6 space group, without the formation of secondary phases or Fe clusters. Fe ions were well integrated, as indicated by fluctuations in lattice parameters, and lattice strain. The crystallite size decreased from 38.42 to 27.54 nm with increasing doping concentration. HRTEM images depicted evenly distributed nanoparticles. At lower dopant concentrations (x = 0.1), smaller and more heterogeneous nanorod-like structures emerged, with average sizes and lengths of 36.56 and 39 nm, respectively. Increasing the doping content to x = 0.2 resulted in a morphological shift towards semi-spherical and ellipsoidal shapes, with average dimensions of 22.84 and 31 nm, respectively. At higher doping levels (x = 0.3), nanoparticles grew to 66.5 nm in size and exhibited a spherical morphology. Raman and Fourier transform infrared spectra showed red-shifting of absorption bands with increasing Fe content, attributed to variations in bond length and Cr/Fe–O–Cr/Fe structural perturbation. XPS and Mössbauer spectroscopy analyses confirmed the oxidation states of Fe3+ and ionized oxygen vacancies in the crystal lattice of Cr2O3 nanoparticles. Higher values of quadrupolar splitting Δ indicated greater structural disorder induced by Fe3+ in octahedral positions and in an oxygen-deficient environment. Atomistic simulations confirmed that Fe3+ dopants can induce the presence of vacancy-complexes, forming a stable double-defect configuration with vacant Cr sites along the c-axis, proximal to oxygen vacancies with a single positive charge. These findings offer both experimental and theoretical insights into the dynamics of structural defects in trivalent transition metal doping of Cr2O3 nanoparticles, which holds significant implications for spintronics research.

The role of surface charge and its decay in surface dielectric barrier discharges

The charge accumulation and decay in surface dielectric barrier discharges (SDBDs) driven by a sine AC voltage waveform (4 kHz) in combination with a nanosecond positive voltage pulse (300 ns, 20 Hz) is experimentally investigated based on a combination of the electro-optical Pockels effect and a high-speed camera. It is found that the accumulation of positive surface charge on the dielectric promotes the discharge in the negative half cycle of the applied AC voltage, whereas it inhibits the development of following new positive charge filaments. The decay of a single positive charge filament on the surface is a result of the neutralization by negative charges that originate either from the migration of negative surface charge (electrons) or the drift of free electrons from the volume above the surface towards the surface. This work aims to contribute to a better understanding of the evolution of surface charge and its effects in SDBDs.

Pagoda[5]arene with Large and Rigid Cavity for the Formation of 1∶2 Host–Guest Complexes and Acid/Base-Responsive Crystalline Vapochromic Properties

Pagoda[5]arene (P5), which is composed of five 2,6-dimethoxylanthracene (2,6-DMA) subunits bridged by methylene groups at 1,5 positions, was conveniently synthesized in 43% by trifluoroacetic acid ...

Observation of Magic Number Clusters from Thermal Dissociation Molecular Dynamics Simulations of Lithium Formate Ionic Clusters.

Molecular dynamics (MD) simulations are well positioned to elucidate the aspects of electrospray ionization (ESI) and high-energy collision dissociation (HCD), as well as give insight into processes that involve neutral species that cannot be observed experimentally in ESI, HCD, and collision-induced dissociation (CID). Here, we utilize temperature dissociation molecular dynamics (TDMD) to model the HCD/CID of lithium formate clusters carrying a single positive charge. These simulations successfully reproduce the experimental ESI HCD spectra of lithium formate solutions and also support the existence of magic number clusters (MNCs) that have been observed. The simulations also provide strong evidence that the main fragmentation channel of such clusters involves neutral (LiHCOO)2 dimers.

Proton Transport in Mitochondrial UCP2 is Regulated by a Matrix-Oriented Salt-Bridge Network

Uncoupling proteins (UCPs) are ion carrier proteins causing regulated proton leak across the mitochondrial inner membrane, thus reducing the rate of ATP synthesis. Despite this important impact, the mechanism of UCP-mediated proton transport has not been fully understood. It has been speculated that the mitochondrial carrier family members contain two interconnected salt-bridge networks facilitating the substrate transport. One of these networks is close to the matrix side (matrix network) and the other is close to the intermembrane space. This study focuses on the role of matrix network on the regulation of proton transport in UCP2. UCP2 and eleven mutants (in matrix network) are expressed recombinantly in the E. coli inner membrane. Six mutants disrupt a single salt-bridge link by maintaining either a single negative (K to Q mutation) or positive (D to N mutation) charge on one end of the salt-bridge (K38Q, K141Q, K239Q, D35N, D138N and D236N). Two mutants (K38Q/K239Q and D138N/D236N) disrupt two salt-bridges, while the other two, lacking three salt-bridges, disrupt the total matrix network (K38Q/K141Q/K239Q and D35N/D138N/D236N). In the last mutant, the matrix network is inversed by switching the salt-bridge forming couples (D35K/K38D/D236K/K239D/D138K/K141D). Results show that the matrix network has a regulatory role, and perturbation of the network increases the rate of proton transport. It seems that individual salt-bridges within the network are cooperatively and equally responsible for regulation of transport. Various alterations of the constituting elements of matrix salt-bridge network do not have a considerable effect on inhibitor-protein interactions. Conformational analysis of the protein (CD and fluorescence) and MD simulations provided molecular insights into the role of UCP2 in proton transport. This study characterizes the physicochemical role of the matrix-oriented salt-bridge network on proton transport in UCP2 and its inhibition by purine nucleotides.

Effect of molybdenum content on the morphology and electronic characteristics of Pd–MoOx nanomaterials and activity evaluation for ethylene glycol electro–oxidation

In this work, Pd–MoOx nanomaterials were developed changing the Mo/Pd precursor ratio and tested for ethylene glycol electro–oxidation reaction (EGOR) in alkaline medium. Mo atomic % compositions of 0, 15, 35, 45 and 75 at. % were evaluated. The increase of Mo at. % resulted in morphology changes due to the directing effect of hexadecyltrimethylammonium bromide (CTAB) on molybdenum passing from hemispheres to nanobelts + hemispheres (15 at. % Mo denoted as Pd85Mo15), then only nanobelts (35 at. % Mo, Pd65Mo35), and nanosheets (45 at. % Mo, Pd55Mo45), and hemispheres were newly obtained at the higher Mo concentration (75 at. % Mo, Pd25Mo75). The activity evaluation of EGOR at 60 °C indicated that Pd25Mo75 supported on Vulcan carbon (Pd25Mo75/C) displayed the highest current density (63.80 mA cm−2), and according with X–ray photoelectron spectroscopy (XPS) the highest activity of Pd25Mo75/C can be related to the abundance of Mo5+ species, which have oxygen vacancies with a single positive charge. Additionally, the analysis of O 1s core–level corroborated the abundance of oxygen with high number of defects sites. Thereby, it was found that Pd loading can be decreased without comprising the activity by increasing oxygen vacancies of MoOx as co–catalyst.

Quadrupole Correction: From Molecular Electrostatic Potential to Free Energies of Halogen Bonding.

Recently several molecular mechanics models of halogen bonding have been published. They describe the electrostatic potential anisotropy near the heavy halogen atom (known as a σ-hole) in different ways, ranging from an all-atom multipole expansion to a single positive extra-point charge. However, the question of a reasonable balance between the accuracy and the simplicity of the model remains open. In this work, we introduce the simplistic RESPQ electrostatics model built on the RESP charges complemented with fixed atomic quadrupoles. We show that it: (1) correctly describes the MEP anisotropy of aromatic halogen atoms, (2) improves the description of the halogen-water interaction energies in both halogen and hydrogen bonding cases, (3) provides an excellent estimation of solvation free energy differences of aromatic halogens, and (4) is compatible (with the help of multipole charge cluster approximation) with contemporary molecular modeling packages.

A highly-simplified and inexpensive MALDI-TOF mass spectrometry sample-preparation method with broad applicability to microorganisms, plants, and insects.

Matrix-assisted laser-desorption and ionization time-of-flight mass spectrometry prepares proteins intact in the gas phase with predominantly a single positive charge. The times-of-flight of charged proteins along a tube held at high vacuum after acceleration in an electrical field are proportional to the square root of the mass-over-charge ratios for the proteins, thereby allowing a mass spectrum to be generated, which can then be used to characterize or identify a protein-containing sample. Several sample-preparation methods are currently available but not all of these are applicable to some forms of fungal biomass and few of these are well suited to the analysis of plant or insect material. We have therefore developed a simplified method that: lyses cells, selectively solubilizes basic proteins, dissolves matrix to a suitable concentration, generates spectra with good intensity and peak richness, costs no more (and generally less) than current methods, and is not constrained in terms of throughput by the availability of centrifuges. Using this method, and a reagent formulation comprising α-cyano-4-hydroxycinnamic acid matrix close to saturation in 60%–65% (v/v) acetonitrile in water containing 2.5% (v/v) trifluoroacetic acid, we have been able to differentiate between strains for a representative subset of aflatoxin-producing and aflatoxin-non-producing strains of Aspergillus fungi, to differentiate between Indian and Pakistani strains of Himalayan balsam rust, to differentiate between closely-related Crassula spp. and regional biotypes of Crassula helmsii, and to differentiate between rubbervine introduced into Australia and Brazil. We have also analyzed fall armyworm and stem-borer samples stored in 70% (v/v) ethanol and old dried insect specimens.

Electrically active induced energy levels and metastability of B and N vacancy-complexes in 4H–SiC

Electrically active induced energy levels in semiconductor devices could be beneficial to the discovery of an enhanced p or n-type semiconductor. Nitrogen (N) implanted into 4H–SiC is a high energy process that produced high defect concentrations which could be removed during dopant activation annealing. On the other hand, boron (B) substituted for silicon in SiC causes a reduction in the number of defects. This scenario leads to a decrease in the dielectric properties and induced deep donor and shallow acceptor levels. Complexes formed by the N, such as the nitrogen-vacancy centre, have been reported to play a significant role in the application of quantum bits. In this paper, results of charge states thermodynamic transition level of the N and B vacancy-complexes in 4H–SiC are presented. We explore complexes where substitutional N/N or B/B sits near a Si (V) or C (V) vacancy to form vacancy-complexes (NV, NV, NV, NV, BV, BV, BV and BV). The energies of formation of the N related vacancy-complexes showed the NV to be energetically stable close to the valence band maximum in its double positive charge state. The NV is more energetically stable in the double negative charge state close to the conduction band minimum. The NV on the other hand, induced double donor level and the NV induced a double acceptor level. For B related complexes, the BV and BV were energetically stable in their single positive charge state close to the valence band maximum. As the Fermi energy is varied across the band gap, the neutral and single negative charge states of the BV become more stable at different energy levels. B and N related complexes exhibited charge state controlled metastability behaviour.

Light Triggered Isoelectric Point and Solubility Shifts Applied to Photoactivated Insulin Depots

We previously described photoactivated insulin depot, a minimally invasive technique of insulin delivery (1). In this approach, an inert photoactivated depot is injected under the skin. Exposure of the depot to light triggers the release of native insulin into the blood. First‐generation materials were designed to have insulin chemically attached to an insoluble polymer (for insolubility) via photocleavable linker. Though this material is effective in studying the approach in vitro and in vivo (2), it has multiple problems associated with the insoluble polymer. About 95% of the depot consisted of the non‐therapeutic polymer, which is non‐biodegradable and difficult to inject into an animal.In this work, we solved these problems by eliminating the polymer and reacting insulin with a photocleavable group containing positively charged groups. The result is an insulin with an altered pI and thus, with a different solubility (3). We achieved the insulin's insolubility by shifting its pI to physiological pH. We observed an increase 0.65 units of pI of insulin with the addition of a single positive charge. We raised the pI of insulin from 5.4 to 7.2, specifically by the addition of two positively charged groups and quenching one negative charge (carboxylate) on insulin. This material has high solubility in acidic pH, and hence can be a soluble formulation. But upon injection at skin pH, it is observed to precipitate as a depot. Upon exposure to light, the positively charged groups are removed to generate the native insulin, which can then be absorbed into the blood due to its high solubility. These materials have high insulin density (91% w/w), are soluble in acidic formulations and upon photolysis, will result in charged, soluble and excretable by‐products without leaving any traces of depot at the site of injection.Support or Funding InformationNIH‐1DP3DK106921‐01, University of Missouri Fast Track Award and UMKC School of Pharmacy Dean's Bridge FundThis abstract is from the Experimental Biology 2018 Meeting. There is no full text article associated with this abstract published in The FASEB Journal.

Effects of surface charge, hydrophilicity and hydrophobicity on functional biocathode catalytic efficiency and community structure

The bioelectrotransformation efficiency of various organic matters and corresponding electrode biofilm community formation as well as electron transfer efficiency in bioelectrochemical systems (BESs) with different modified electrodes has been extensively studied on the anode side. However, the effects of cathode interface characteristics towards the BESs bioelectrotransformation performance remain poorly understood. In this study, the nitrobenzene-reducing biocathode catalytic efficiency and community structure in response to different modified electrodes (control: hydrophobic and no charge; –SH: hydrophobic and single negative charge; –NH2: hydrophilic and single positive charge –NH–NH2: hydrophilic and double positive charges) were investigated. The biocathode transformation efficiency of nitrobenzene (NB) to aniline (AN) (ENB-AN) was affected by the nature of electrode interface as well as the biocathode community formation and structure. Cathodes with hydrophilic surface and positive charges have performed well in the bioelectrotransformation experiments, and especially made an outstanding performance when inorganic NaHCO3 was supplied as carbon source and cathode as the sole electron donor. Importantly, the hydrophilic surfaces with positive charges were dominated by the electroactive nitroaromatic reducers (Enterococcus, Desulfovibrio and Klebsiella) with the relative abundance as high as 72.20 ± 1.87% and 74.86 ± 8.71% for –NH2 and –NH–NH2 groups respectively. This could explain the higher ENB-AN in the hydrophilic groups than that of the hydrophobic –SH modified group. This study provides new insights into the effects of electrode interface characteristics on the BESs biocathode performance and offers some suggestions for the future design for the improvement of bioelectroremediation performance.

Electronic structure of Li+@C60: Photoelectron spectroscopy of the Li+@C60[PF6−] salt and STM of the single Li+@C60 molecules on Cu(111)

We report the scanning tunneling microscope (STM) observation of the Li+ ion endohedral C60 on Cu(111), prepared by means of evaporation of a high-purity Li+@C60[PF6−] salt. The electronic state of Li+@C60 in the Li+@C60[PF6−] salt was also determined using photoemission and X-ray absorption spectroscopy, along with the density functional theory (DFT) calculations. In the salt, Li and PF6 had nearly single positive and negative charge, respectively; thus the C60 cage was practically neutral. The salt decomposed under ultra-high vacuum while heating at 400 °C. This allowed the selective deposition of Li+@C60 on Cu(111). Although secondary-ion mass spectroscopy of the deposited Li+@C60 film showed a decrease in the Li-content during evaporation, Li+@C60 was successfully identified using STM. The DFT calculations of Li+@C60 on Cu(111) suggested that the Li+ ion was singly charged and the location of the Li+ ion was displaced in an upward direction, which altered the local density of states in an upper section of C60, especially for LUMO+2. The calculated results were mostly in agreement with the bias-dependent STM and dI/dV images. However, an inconsistency was observed between the calculation and experiments in case of empty state imaging where tip-induced displacement of the Li+ ion may occur.

Polarization, donor-acceptor interactions, and covalent contributions in weak interactions: a clarification.

The concepts of polarization (induction), charge transfer and covalent bonding contributions are discussed in terms of weak interactions. They are shown to be different incarnations of the same phenomenon, so that using polarization to describe them is most consistent as it is the only real, measurable and uniquely defined quantity of the three. Dispersion is discussed as a form of polarization within the Feynman description. Model calculations are described. Graphical abstract The electron density of a hydride ion (nucleus white) polarized by a single positive point charge (brown).

Stereospecificity of the Hofmann elimination in the gas phase.

The Hofmann elimination of ammonium ions having a single positive charge is demonstrated to exhibit stereospecificity with regard to expulsion of neutral alkene. For the 3-hexyl series of threo and erythro 4-monodeuterated ions (3-hexylammonium ion; N,N,N-trimethyl- d3-3-hexylammonium ion; N-ethyl-3-hexylammonium ion; N-methyl, N-ethyl-3-hexylammonium ion; N,N-dimethyl, N-ethyl-3-hexylammonium ion), the upper limit of the E:Z ratio of the expelled alkene (r) approaches 2 (the stereospecificity) with a deuterium isotope effect close to 2.0, although the effects of isotopic substitution diminish the E:Z ratio somewhat. Two fragmentations compete with that reaction: hydride shift (which gives the same products but with hydrogen scrambling) and loss of a neutral amine to give an alkyl cation. These competing reactions render our calculation approximate, but the results suggest a value not too far from the upper limit.

ESI-MS of Cucurbituril Complexes Under Negative Polarity.

Electrospray ionization mass spectrometry (ESI-MS) is a powerful tool to study host-guest supramolecular interactions. ESI-MS can be used for detailed gas-phase reactivity studies, to clarify the structure, or simply to verify the formation of complexes. Depending on the structure of the host and of the guest, negative and/or positive ESI are used. Here we report the unexpected formation of host-guest complexes between cucurbit[n]urils (n = 7, 8, CB[n]) and amine, styryl pyridine, and styryl pyridine dimer cations, under negative ESI. Non-complexed CB[n] form double charged halide (Br-, Cl-, F-) adducts. Under negative ESI, halide ions interact with CB[n] outer surface hydrogen atoms. One to one host-guest complexes (1:1) of CB[n] with positive charged guests were also observed as single and double charged ions under negative ESI. The positive charge of guests is neutralized by ion-pairing with halide anions. Depending on the number of positive charges guests retain in the gas phase, one or two additional halide ions are required for neutralization. Complexes 1:2 of CB[8] with styryl pyridines retain two halide ions in the gas phase, one per guest. Styryl pyridine dimers form 1:1 complexes possessing a single extra halide ion and therefore a single positive charge. Negative ESI is sensitive to small structural differences between complexes, distinguishing between 1:2 complexes of styryl pyridine-CB[8] and corresponding 1:1 complexes with the dimer. Negative ESI gives simpler spectra than positive ESI and allows the determination of guest charge state of CB[n] complexes in the gas phase. Graphical Abstract ᅟ.

Thermophilic Ferritin 24mer Assembly and Nanoparticle Encapsulation Modulated by Interdimer Electrostatic Repulsion.

Protein cage self-assembly enables encapsulation and sequestration of small molecules, macromolecules, and nanomaterials for many applications in bionanotechnology. Notably, wild-type thermophilic ferritin from Archaeoglobus fulgidus (AfFtn) exists as a stable dimer of four-helix bundle proteins at a low ionic strength, and the protein forms a hollow assembly of 24 protomers at a high ionic strength (∼800 mM NaCl). This assembly process can also be initiated by highly charged gold nanoparticles (AuNPs) in solution, leading to encapsulation. These data suggest that salt solutions or charged AuNPs can shield unfavorable electrostatic interactions at AfFtn dimer-dimer interfaces, but specific "hot-spot" residues controlling assembly have not been identified. To investigate this further, we computationally designed three AfFtn mutants (E65R, D138K, and A127R) that introduce a single positive charge at sites along the dimer-dimer interface. These proteins exhibited different assembly kinetics and thermodynamics, which were ranked in order of increasing 24mer propensity: A127R < wild type < D138K ≪ E65R. E65R assembled into the 24mer across a wide range of ionic strengths (0-800 mM NaCl), and the dissociation temperature for the 24mer was 98 °C. X-ray crystal structure analysis of the E65R mutant identified a more compact, closed-pore cage geometry. A127R and D138K mutants exhibited wild-type ability to encapsulate and stabilize 5 nm AuNPs, whereas E65R did not encapsulate AuNPs at the same high yields. This work illustrates designed protein cages with distinct assembly and encapsulation properties.

Multiplex Paper-Based Colorimetric DNA Sensor Using Pyrrolidinyl Peptide Nucleic Acid-Induced AgNPs Aggregation for Detecting MERS-CoV, MTB, and HPV Oligonucleotides.

The development of simple fluorescent and colorimetric assays that enable point-of-care DNA and RNA detection has been a topic of significant research because of the utility of such assays in resource limited settings. The most common motifs utilize hybridization to a complementary detection strand coupled with a sensitive reporter molecule. Here, a paper-based colorimetric assay for DNA detection based on pyrrolidinyl peptide nucleic acid (acpcPNA)-induced nanoparticle aggregation is reported as an alternative to traditional colorimetric approaches. PNA probes are an attractive alternative to DNA and RNA probes because they are chemically and biologically stable, easily synthesized, and hybridize efficiently with the complementary DNA strands. The acpcPNA probe contains a single positive charge from the lysine at C-terminus and causes aggregation of citrate anion-stabilized silver nanoparticles (AgNPs) in the absence of complementary DNA. In the presence of target DNA, formation of the anionic DNA-acpcPNA duplex results in dispersion of the AgNPs as a result of electrostatic repulsion, giving rise to a detectable color change. Factors affecting the sensitivity and selectivity of this assay were investigated, including ionic strength, AgNP concentration, PNA concentration, and DNA strand mismatches. The method was used for screening of synthetic Middle East respiratory syndrome coronavirus (MERS-CoV), Mycobacterium tuberculosis (MTB), and human papillomavirus (HPV) DNA based on a colorimetric paper-based analytical device developed using the aforementioned principle. The oligonucleotide targets were detected by measuring the color change of AgNPs, giving detection limits of 1.53 (MERS-CoV), 1.27 (MTB), and 1.03 nM (HPV). The acpcPNA probe exhibited high selectivity for the complementary oligonucleotides over single-base-mismatch, two-base-mismatch, and noncomplementary DNA targets. The proposed paper-based colorimetric DNA sensor has potential to be an alternative approach for simple, rapid, sensitive, and selective DNA detection.

Spontaneous Mass and Charge Losses from Single Multi-Megadalton Ions Studied by Charge Detection Mass Spectrometry.

Spontaneous mass and charge losses from individual multi-megadalton ions have been observed with charge detection mass spectrometry (CDMS) by trapping single hepatitis B virus (HBV) capsids for 3s. Gradual increases in the oscillation frequency of single ions in the ion trap are attributed mainly to mass loss (probably solvent, water, and/or salt). The total mass lost during the 3s trapping period peaks at around 20kDa for 4MDa HBV T = 4 capsids. Discrete frequency drops punctuate the gradual increases in the oscillation frequencies. The drops are attributed to a sudden loss of charge. In most cases a single positive charge is lost along with some mass (on average around 1000Da). Charge loss occurs for over 40% of the trapped ions. It usually occurs near the beginning of the trapping event, and it occurs preferentially in regions of the trap with strong electric fields, indicating that external electric fields promote charge loss. This process may contribute to the decrease in m/z resolution that often occurs with megadalton ions. Graphical Abstract ᅟ.

Lipases That Activate at High Solvent Polarities.

Thermomyces lanuginosus lipase (TlL) and related lipases become activated in low-polarity environments that exist at the water-lipid interface where a structural change of the "lid" region occurs. In this work, we have investigated the activation of TlL (Lipase_W89) and certain lid mutants, containing either a single positive charge mutation, E87K (Lipase_K87_W89), within the lid region or a lid residue composition of both lipase and esterase character (Hybrid_W89) as a function of solvent polarity. Activation differences between the variants and TlL were studied by a combination of biophysical and theoretical methods. To investigate the structural changes taking place in the lid region upon lipase activation, we used a fluorescence-based method measuring the efficiency of Trp89 in the lid to quench the fluorescence of a bimane molecule attached in front (C255) and behind (C61) the lid. These structural changes were compared to the enzymatic activity of each variant at the water-substrate interface and to theoretical calculations of the energies associated with lid opening as a function of the dielectric constant (ε) of the environment. Our results show that the lid in Lipase_K87_W89 undergoes a pronounced structural transition toward an open conformation around ε = 50, whereas only small changes are detected for Lipase_W89 ascribed to the stabilizing effect of the positive charge mutation on the open lid conformation. Interestingly, Hybrid_W89, with the same charge as Lipase_W89, shows a stabilization of the open lid even more pronounced at high solvent polarities than that of Lipase_K87_W89, allowing activation at ε < 80. This is further indicated by measurement of the lipase activity for each variant showing that Hybrid_W89 is more quickly activated at the water-lipid interface of a true, natural substrate. Combined, we show that a correlation exists between structural changes and enzymatic activities detected on one hand and theoretical calculations on lid opening energies on the other. These results highlight the key role that the lid plays in determining the polarity-dependent activation of lipases.

A computational study of dicationic ionic liquids/CO₂ interfaces.

Recent studies on CO2 capture using dicationic ionic liquids (DILs) demonstrated that DILs are promising absorbents for CO2 uptake especially compared with monocationic ionic liquids (MILs) analogues, in which each cation carries single positive charge in contrast to two unit charges of a dication. However, DILs/CO2 interfacial properties at the molecular level are still unknown. This work investigated the CO2 absorption properties of representative DILs, 1-alkyl-3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide, [Cn(mim)2](Tf2N)2 (n = 3, 6, 12), using molecular dynamics (MD) simulations. The higher interfacial CO2 density at DIL than that at MIL interfaces suggests the increased CO2 interaction sites in DILs. The interfacial CO2 density also exhibits an alkyl chain length dependence which decreases with the elongation of alkyl chain and proportionally correlates with the content of fluorine atoms at interfaces. Different alkyl chain orientations in DILs were illustrated in contrast to those of MILs; both DILs and CO2 inside DILs exhibit lower diffusivity than MILs, in agreement with the stronger cation-anion binding energy of DILs. Moreover, DILs show a lower H2O and N2 uptake from flue gas compared with MILs, implicating the higher CO2/H2O and CO2/N2 selectivity.