Ionic Components Research Articles

In Search of Entangled Singlet Pure Diradicals.

Recent work has documented conjugate polycyclic hydrocarbons presenting unusual properties: accepting full on-bond electron pairing, they could be considered as closed-shell architectures, but their ground-state wave function is actually a pure diradical singlet, free of any ionic component, in contrast to diradicaloids. These so-called entangled molecules also differ from disjoint diradicals, which do not accept on-bond electron pairing, in that their singly occupied molecular orbitals (SOMOs) are spatially entangled rather than disjoint. The present work first extends the study to a broad series of architectures exhibiting the same properties, namely: they present two degenerate SOMOs in the topological Hückel Hamiltonian, and their pure diradical wave functions lead to symmetry-keeping geometries. These solutions are always of lower energy than the closed-shell solutions that break symmetry and destroy aromaticity of some six-membered rings. A topological criterion ensuring that a given conjugate hydrocarbon will behave as an entangled pure diradical is then formulated. Next, a second set of molecules is proposed, still exhibiting two degenerate Hückel SOMOs, but with smaller contrast between the energies of open-shell and closed-shell solutions. Conservation of six-membered rings aromaticity appears as the driving factor ruling the stability of diradical solutions.

Synthesis and Structural Characterization of 2,2’-Bipyridine Zinc Formate: Analysis of Formate Bonding and Hydrosilylation of CO2 and Carbonyl Compounds

The zinc formate compound (bipy)Zn(O2CH)2 is obtained via the reaction of Zn(O2CH)2 with 2,2’-bipyridine (bipy). In addition, (bipy)Zn(O2CH)2 may be formed from zinc hydride via addition of bipy followed by addition of (i) HCO2H and (ii) CO2. The molecular structure of (bipy)Zn(O2CH)2 has been determined by X-ray diffraction, thereby demonstrating that it exists as a monomeric species with a distorted tetrahedral zinc center and κ1-monodentate formate ligands. As such, the coordination environment of the zinc provides a contrast to the octahedral sites in the isomeric 4,4’-bipyridine counterpart, (bipy4,4’)Zn(O2CH)2, and the aqua derivative, (bipy)Zn(O2CH)2(OH2)•H2O, both of which feature bridging formate ligands. Analysis of the bonding within the formate ligand indicates that the zinc–formate moiety is not best represented by a Zn–O–C(=O)H resonance structure, but instead possesses a significant ionic component that reduces the C=O bond order and increases the C–O bond order. The formate compound (bipy)Zn(O2CH)2 participates in hydrosilylation transformations involving CO2 and carbonyl compounds, including (i) the reaction of CO2 with (MeO)3SiH to afford HCO2Si(OMe)3 and (ii) insertion of Ph2CO, PhC(O)Me, Me2CO and PhCHO into the Si–H bonds of PhSiH3 to afford PhSi[OCH(R)R’]3via PhSiH2[OCH(R)R’] and PhSiH[OCH(R)R’]2.

Insight into groundwater quality change before and after the 2016 Kumamoto earthquake

The Kumamoto Earthquake is named after the Kumamoto Prefecture where the series of earthquakes occurred in the city located on the island of Kyushu, in southwest Japan.In this area, 100 % of the population depends on groundwater for drinking water; hence, groundwater is an extremely important lifeline for people. The effect of earthquakes on the water quality of groundwater has been suggested based on monitoring data measured by public agencies once or twice a year. Frequent water quality monitoring of the groundwater in the Kumamoto area has continued once a month for six years since 2014. In this study, we aimed to statistically evaluate the changes in groundwater quality caused by the 2016 earthquake and provide further insights into its mechanisms. The Stiff diagrams using major ionic components showed no apparent overall water quality change before and after the earthquake for 14 groundwater samples in the area. However, statistically significant changes were indicated for 11 samples by k-medoids clustering (non-hierarchical cluster analysis), divided into two clusters before and after the earthquake. In addition, the samples showing water quality changes did not vary even over the four years after the earthquake, indicating that the change was not temporal. The magnitude and trend of the change in individual water quality parameters depended on the sampling sites, while some parameters, such as nitrate, showed seasonal fluctuations due to precipitation conditions more than the effect of the earthquake. No particular relationship was found between the distance from the sampling sites to the epicenters or active faults and the degree of water quality changes. Finally, it was considered that the aquifer breaching/fluid mixing model (AB/FM model), through the change in the bleeding channel of water due to seismic shaking, most likely explains the main mechanism of water quality change in groundwater in the Kumamoto area.

Characteristics of tritium, stable isotopes and chemical components in monthly precipitation at Hiroshima, Japan.

This article mainly discusses tritium concentrations in monthly precipitation at Hiroshima City during 2021. The tritium concentrations, which were measured with a low background liquid scintillation counter, fluctuated from 0.16 to 0.78BqL-1. Additionally, hydrogen and oxygen stable isotopes and ionic species were measured in order to characterize precipitation, and their trends including tritium concentrations were compared with data collected in other regions of Japan in previous studies. Although the results showed the characteristics of precipitation were similar to those observed in the other regions, the tritium concentrations were found to be contrary to behavior expected from the latitude effect and some of the observed ionic components were suggested to be continental in origin. Since these results are not common at other sites in Japan, the tritium concentration in the westernmost region of Honshu, including Hiroshima City, may be influenced by Asian continental influences.

Lipid nanoparticles as adjuvant of norovirus VLP vaccine augment cellular and humoral immune responses in a TLR9- and type I IFN-dependent pathway.

Norovirus (NoV) virus-like particles (VLPs) adjuvanted with aluminum hydroxide (Alum) are common vaccine candidates in clinical studies. Alum adjuvants usually inefficiently assist recombinant proteins to induce cellular immune responses. Thus, novel adjuvants are required to develop NoV vaccines that could induce both efficient humoral and robust cellular immune responses. Lipid nanoparticles (LNPs) are well-known mRNA delivery vehicles. Increasing evidence suggests that LNPs may have intrinsic adjuvant activity and can be used as adjuvants for recombinant protein vaccines; however, the underlying mechanism remains poorly understood. In this study, we compared the adjuvant effect of LNPs and Alum for a bivalent GI.1/GII.4 NoV VLP vaccine. Compared with Alum, LNP-adjuvanted vaccines induced earlier production of binding, blocking, and neutralizing antibodies and promoted a more balanced IgG2a/IgG1 ratio. It is crucial that LNP-adjuvanted vaccines induced stronger Th1-type cytokine-producing CD4+ T cell and CD8+ T cell responses than Alum. The adjuvant activity of LNPs depended on the ionizable lipid components. Mechanistically, LNPs activated innate immune responses in a type I IFN-dependent manner and were partially dependent on Toll-like receptor (TLR) 9, thus affecting the adaptive immune responses of the vaccine. This conclusion was supported by RNA-seq analysis and in vitro cell experiments and by the deeply blunted T cell responses in IFNαR1-/- mice immunized with LNP-adjuvanted vaccines. This study not only identified LNPs as a high quality adjuvant for NoV VLP vaccines, but also clarified the underlying mechanism of LNPs as a potent immunostimulatory component for improving protein subunit vaccines.IMPORTANCEWith the rapid development of mRNA vaccines, recurrent studies show that lipid nanoparticles (LNPs) have adjuvant activity. However, the mechanism of its adjuvant effect in protein vaccines remains unknown. In this study, we found that the LNP-adjuvanted norovirus bivalent virus-like particle vaccines led to durable antibody responses as well as Th1-type cytokine-producing CD4+ T cell and CD8+ T cell responses, which exceeded the efficiency of the conventional adjuvant aluminum hydroxide. Mechanistically, LNPs activated innate immune responses in a type I IFN-dependent manner and were partially dependent on Toll-like receptor 9, thus affecting the adaptive immune responses of the vaccine. This work unveils that LNPs as a potent immunostimulatory component may be ideal for generating CD8+ T cell and B cell responses for recombinant protein vaccines.

Alfvén wave generation and electron energization in the KiNET-X sounding rocket mission

Active plasma experiments can be used to strongly perturb the space plasma environment. During the early phase of a chemical release (e.g., few to several seconds), the injected plasma cloud can excite a variety of waves rather than acting as “inert” tracer particles. It is during this early phase of the release that fundamental plasma processes can be studied. For example, the Trigger [Holmgren et al., J. Geophys. Res. 85, 5043 (1980)] and recent KINetic-scale Energy and momentum Transport eXperiment (KiNET-X) missions were both designed to study processes related to auroral electron energization. Early experiments relied primarily on ground-based optics to diagnose the plasma interaction. Advances in optical sensors have dramatically improved imaging capability of both the ion and neutral components of the injected cloud; therefore, optics remain an important part of these types of experiments. However, advances in plasma (fields and particles) instruments have enabled a new generation of possible experiments from the sounding rocket platform. In this article, we discuss previous sounding rocket (and orbital) active experiments, the related science objectives, and an overview of select results from the KiNET-X rocket mission. Specifically, KiNET-X produced an Alfvénic perturbation, a variety of high frequency waves, energized thermal electrons, and produced a field-aligned electron beam of ∼ 200 eV. The electron energization indicates non-ideal coupling of the injected barium cloud with the ambient ionospheric plasma.

Electron work function guided tailoring of (W4-x, Mx)C4 /doped Ni matrix interfacial bonding: Insights from first-principles calculations

Heavy tungsten carbide (WC) may cause inhomogeneous distributions in WC-metal matrix composite hardfacing overlays, thus negatively affecting its performance as reinforcement. WC can be lightened by partially substituting W with lighter metals, e.g., Mo and Cr, while maintaining its strength. However, the bonding between modified WC and matrix metals such as nickel (a typical metal-matrix for overlays) is uncertain. This article reports a study on the interfacial bonding between (W4-x, Mx)C4 (M=Mo or Cr) and Ni matrix via first-principle calculations. Different atomic interactions i.e., metal-metal and metal-carbon interactions, at the interface were studied to understand the interfacial bonding through analyses of electron work function (EWF), electron localization function, electronic density of states, bond order, and net charge. It was demonstrated that the lighter (W4-x, Mx)C4 carbides exhibit strong bonding with Ni, comparable to or even stronger than that of WC/Ni interface, and the interfacial bonding includes covalent, ionic and metallic bond components. It is demonstrated that the interfacial bonding can be tuned by doping elements in the Ni matrix with different EWFs, e.g., Mn, Cu, Au, Pt, and Se. Efforts have been made to verify a hypothesis that EWF is an indicator, which can be used to guide selecting effective dopants for tailoring the interfacial bond strength.

Preparation and Evaluation of Metformin Microspheres by Ionotropic Gelation Method

The purpose of this study was to formulate metformin microsphere in order to lessen its undesirable effects. To prepare metformin microspheres, the ionotropic gelation technique was used. In this process, two ionic components interact under specific circumstances. There needs to be a polymer in at least one of these two ionic components. Microspheres are formed by the simple interaction of an ionic polymer with an oppositely charged ion. In this procedure, the polymers employed were sodium alginate and chitosan; calcium chloride was used for the crosslinking process. Various parameters like particle size, Percentage yield, swelling index, Drug entrapment efficiency, Drug release study (In- vitro) and drug release kinetics studies were performed. From the experimental data it has been shown that chitosan and calcium chloride plays important role for variation of characteristic parameters of microspheres.

Unlocking Nanoprecipitation: A Pathway to High Reversibility in Nanofluidic Memristors.

Solid-state nanochannels have emerged as a promising platform for the development of ionic circuit components with analog properties to their traditional electronic counterparts. In the last years, nanofluidic devices with memristive properties have attracted special interest due to their applicability in, for example, the construction of brain-like computing systems. In this work, an asymmetric track-etched nanofluidic channel with memory-enhanced ion transport is reported. The results illustrate that the formation of nanoprecipitates on the channel walls induces memory effects in ion transport, leading to characteristic hysteresis loops in the current-voltage curves, a hallmark of memristive behavior. Notably, these memristive properties are achievable with a straightforward experimental setup that combines an aqueous solvent and a relatively low-soluble inorganic salt. The various conductance states can be rapidly and reversibly tuned over prolonged time scales. Furthermore, under appropriate measurement conditions, the nanofluidic device can alternate between different iontronic regimes and states, encompassing ion current rectification, ON-OFF states, and memristor-like behavior. These findings provide insights into the design and optimization of nanofluidic devices for bioinspired ionic circuit components.

Optical, dielectric, and rheological properties of EG-Al2O3/AgNO3 nanofluids: Insights and advances in multifunctional materials for soft device technologies

Nanofluids (NFs) of fascinating multifunctional properties are the advanced materials highly admired in emerging soft device technologies. In this innovative research, we explored the detailed optical, dielectric, and rheological properties of silver ions conducting green NFs. These NFs comprise ethylene glycol (EG) as viscous base fluid, suspension of a fixed amount (0.02 wt%) aluminum oxide (Al2O3) nanoparticles for high performance thermal conductor, and addition of silver nitrate (AgNO3) salt as the ionic component of varying amounts ranging from 0.2 to 2.0 wt% are prepared and investigated. The detailed analysis of 200–800 nm wavelength range ultraviolet–visible (UV–Vis) absorbance spectra of these EG–Al2O3/AgNO3 based NFs demonstrated their significant photosensitivity character in the visible region, radiations shielding performance in the UV region, and trio energy band gaps in a wide semiconducting range from 2.4 to 4.9 eV which are found adequately tunable with the AgNO3 concentrations. The high static dielectric permittivity (εs ≈ 40) of these polar NFs, at 298.15 K, showed a marginal change with the variation in AgNO3 concentrations confirming a little alteration in the parallel aligned dipole ordering of hydrogen bonded EG molecular network beside the ion-molecules-nanoparticle interactions and formation of ion-dipole complexes (coordinative interaction). The electrical conductivity of EG–Al2O3 NF increased by three orders of magnitude i.e., from 10−6 to 10−3 S/cm, at the initial addition of 0.2 wt% AgNO3 in it and then, exhibited almost a linear increase with further increasing the salt concentrations up to 2.0 wt% realizes them promising ionic nanofluids. Rheological investigations on these NF samples, at 298.15 K, validate their Newtonian behaviour with a high dynamic viscosity of 14 mPa s. These experimental findings highlight the multifunctional characteristics of EG–Al2O3/AgNO3 nanofluids which could be utilized in heat transfer, solar energy harvesting/storage, and the development of next-generation iontronic and optoelectronic devices and silver ion conducting biomedical sensors.

AGN STORM 2. IX. Studying the Dynamics of the Ionized Obscurer in Mrk 817 with High-resolution X-Ray Spectroscopy

We present the results of the XMM-Newton and NuSTAR observations taken as part of the ongoing, intensive multiwavelength monitoring program of the Seyfert 1 galaxy Mrk 817 by the AGN Space Telescope and Optical Reverberation Mapping 2 (AGN STORM 2) Project. The campaign revealed an unexpected and transient obscuring outflow, never before seen in this source. Of our four XMM-Newton/NuSTAR epochs, one fortuitously taken during a bright X-ray state has strong narrow absorption lines in the high-resolution grating spectra. From these absorption features, we determine that the obscurer is in fact a multiphase ionized wind with an outflow velocity of ∼5200 km s−1, and for the first time find evidence for a lower ionization component with the same velocity observed in absorption features in the contemporaneous Hubble Space Telescope spectra. This indicates that the UV absorption troughs may be due to dense clumps embedded in diffuse, higher ionization gas responsible for the X-ray absorption lines of the same velocity. We observe variability in the shape of the absorption lines on timescales of hours, placing the variable component at roughly 1000 R g if attributed to transverse motion along the line of sight. This estimate aligns with independent UV measurements of the distance to the obscurer suggesting an accretion disk wind at the inner broad line region. We estimate that it takes roughly 200 days for the outflow to travel from the disk to our line of sight, consistent with the timescale of the outflow's column density variations throughout the campaign.

Three-dimensional transient modeling and simulation of high-current multi-component vacuum arc under transverse magnetic field

This paper established a three-dimensional transient MHD model of a high-current multi-component vacuum arc under a transverse magnetic field (TMF) to simulate the dynamic characteristics of plasma parameters in the uniform motion mode of a contracted arc under lower TMF. The model considered the ionization–recombination process among the multi-components and used the P1 model to calculate the thermal radiation losses. The simulation results show that the ion number density of The TMF arc is on the order 1024 m−3, and when the plasma temperature reaches 4.3 eV, the effects of thermal radiation cannot be ignored. The majority of the plasma from the cathode and anode undergo acceleration and then deceleration before finally intersecting at the center of the arc, creating an extreme value of the density and the pressure, where a large amount of kinetic energy is converted into internal energy. The arc will be bent and deflected under the action of the ampere force, and the deflection of Cu3+ is especially obvious. The TMF affects the collision strength of the jet in the intersection area and, thus, affects the ion density, in which the change of Cu2+ is dominant. The ionization–recombination process of ions is mainly determined by the electron temperature, which is affected by the arc current. As the current decreases, Cu1+ increases and Cu2+ and Cu3+ decrease, and the change in ionization rate is the main reason for the change in the proportion of each ionic component; the heat flux density to the anode and cathode is on the order of 1010 W/m2, which heats the front of the arc and ensures the stable movement of the arc. Meanwhile, due to the high ion number density, the ion heat flux accounts for the main part of the heat flux, and the anode exhibits a higher proportion of ion heat flux.

Ionic Components of Particulate Matter 2.5 May Influence Daily Prevalence of Skin Symptom Exacerbations in Allergy Sufferers

(1) Background: To date, little research has epidemiologically examined whether the concentration of particulate matter (PM) 2.5 and its ionic components is related to the prevalence of skin symptom exacerbations. Therefore, this study aimed to clarify this association in patients with allergic diseases. (2) Methods: From 1 February to 31 May 2020, we evaluated the daily prevalence of skin symptoms in outpatients with allergic diseases being treated at Fukuoka National Hospital, Fukuoka, Japan, and measured the concentration of PM2.5 and its ionic components. (3) Results: Univariate analysis showed a statistically significant association between skin symptoms and the concentration of PM2.5 and the ionic components SO42−, NH4+, K+, and Mg2+; multivariate analysis showed a statistically significant association between the daily prevalence of skin symptom and the concentration of the ionic components SO42− or Mg2+. (4) Conclusions: Our findings indicate that the concentration of some PM2.5 ionic components may affect skin symptom in patients with allergic diseases.

Lipid digestion profiles of pickering emulsion gels stabilized by β-glucans microgel particles

Pickering emulsion gels (PEGs) stabilized by microgel particles (MPs) have a wide range of applications. However, the extent and mechanisms of lipid digestion in these PEGs are still unclear. In this study, we explored how the concentration of β-glucans MPs and different stabilizers influence the lipid digestion profiles. Our findings revealed a significant role of β-glucans MPs in modulating lipid digestion, with a reduction in lipid digestion rate and extent correlated with an increase in MPs concentration. Notably, compared to droplets stabilized by other agents, emulsions stabilized by β-glucans MPs exhibited the lowest initial release rate (0.81 ± 0.08 FFA%/min) and final degree of digestion (18.96% ± 0.42%) of free fatty acids. Lipid droplets stabilized by β-glucan MPs were able to effectively resist the effects of high ionic strength and complex components in the oral and gastric environments, maintaining their structural integrity and preventing droplet aggregation. Our results indicated that β-glucans MPs are not only effective stabilizers but also provide a novel approach to controlling lipid digestibility.

Volumetric 3D printing of ionic conductive elastomers for multifunctional flexible electronics

Flexible electronics based on ionic conductive elastomers (ICE) hold significant potential for applications in smart wearables, self-powered sensing, and human-computer interaction. However, current fabrication techniques constrain ICE-based ionic electronic components to simplified volumetric geometries, limiting their functionality. This work reports a volumetric 3D printing (V3DP) for fabricating flexible electronic components with excessive transparency, high conductivity, excellent thermal stability, and superior adhesion. By controlling the light dose, this printing technique enables precise modulation of the printed structures' mechanical properties. Furthermore, V3DP greatly improves the processing efficiency of high-viscosity ionic conductive liquids and makes it easier to prepare composite structures, combining different conductive mechanisms through unique overprinting. This study provides a promising strategy for preparing multifunctional, liquid-free, ionic flexible electronics, such as strain sensors and ionic-electronic triboelectric nanogenerators (iTENG).

Toward the Chemical Structure of Diborane: Electronic Force Density Fields, Effective Electronegativity, and Internuclear Turning Surface Properties.

The chemical structure of diborane was elucidated through the superposition of the vector fields of the electron density gradient ∇ρ(r), the electrostatic force Fes(r), and the kinetic force Fk(r), together with the analysis of the cumulative charges of the atoms and pseudoatoms delimited in the aforementioned fields. It was proposed that the Fk-pseudoatomic charge could be employed as a metric for quantifying the ionic component of a related atomic charge. The electron permeability across an internuclear turning surface─specifically, the zero-flux surface in Fk(r)─was characterized by probing it through mapping the total static potential φem(r). The conceptualization of post hoc electronegativity was presented for consideration. Our analysis revealed that the ordinary B-H and bent B-μ-H bonds in diborane demonstrate the polar covalent character with minor contributions of the ionic component. The former bond exhibits a greater electron permeability through the internuclear turning surface, indicating a stronger tendency for electron sharing between the corresponding nucleus-dominated regions. The electron density accumulation along the bent B-μ-H bond path diverges from the minimum action trajectories of the forces Fes(r) and Fk(r). This phenomenon can be associated with the structural strain within the angled, three-center two-electron bonding B-μ-H-B. The internuclear B···B paths were identified in Fes(r) and Fk(r), in contrast to ∇ρ(r). This fact, in conjunction with a pronounced electron permeability through the mutual turning surface between the two boron nuclei, implies a certain degree of electron exchange between the boron-dominated pseudoatomic regions. Furthermore, the anomalous [B-]H···μ-H intermolecular polar interactions were described between the strongly negatively charged hydrogen atoms in the monoclinic crystalline β-phase of diborane. In fact, the ionic contributions to the charges of the hydrogen atoms are shown to be relatively small.

Ionizable Lipid Containing Nanocarriers for Antimicrobial Agent Delivery

Antimicrobial resistance (AMR) poses a global health crisis demanding innovative solutions. Traditional antibiotics, though pivotal over the past century in combating bacterial infections, face diminished efficacy against evolving bacterial defense mechanisms, especially in Gram‐negative strains. This study explores self‐assembled ionizable lipid nanoparticles (LNPs) with the incorporation of two ionizable lipid components (one cationic, one anionic) in nanocarriers for advanced antimicrobial drug delivery of the broad‐spectrum antibiotic Piperacillin (Pip). Incorporating cationic ionizable lipid ALC‐0315, recognized as a functional lipid in the Pfizer‐BioNTech mRNA‐based SARS‐CoV‐2 vaccine, into LNPs allowed mesophase transition, pH responsiveness, and ionization behavior in acidic environments found in sites of bacterial infections, to be studied using synchrotron small angle X‐ray scattering, dynamic light scattering, and a 2‐(p‐toluidino)‐6‐naphthalene sulfonic acid assay. Incorporating another anionic ionizable lipid, oleic acid not only modulates the LNPs’ physicochemical properties, such as size, internal phase nanostructure, and surface charge but also synergistically enhances the antimicrobial potency together with ALC‐0315 with a benefit enhancing permeability and fusion with bacterial membranes. This study introduces a strategy for tailoring ionizable lipid compositions in LNPs, providing a new approach to antimicrobial treatment contributing to the fight against AMR.

(Invited) Bio-Inspired Time Varying Networks for Novel Computing Primitives

As a result of a hundred million years of evolution, living animals have adapted extremely well to their ecological niche. Such adaptation implies species-specific interactions with their immediate environment by processing sensory cues and responding with appropriate behavior. Understanding how living creatures perform pattern recognition and cognitive tasks is of particular importance for computing architectures: by studying these information pathways refined over eons of evolution, researchers may be able to streamline the process of developing more highly advanced, energy efficient autonomous systems.With the advent of novel electronic and ionic components along with a deeper understanding of information pathways in living species, a plethora of opportunities to develop completely novel information processing avenues are within reach.Basal biological principles are highlighted, including phylogenies, ontogenesis, and homeostasis, with particular emphasis on network topology and dynamics. While in machine learning, system training is performed on virgin networks without any a priori knowledge, the approach proposed here distinguishes itself unambiguously by employing growth mechanisms as a guideline to design novel computing architectures. Within this framework, experiments on low-frequency relaxation type oscillators coupled via complex time-varying networks will be presents. The spatio-temporal development of the network results from a mutual interaction between the oscillator ensemble and the network structure. The blooming and pruning of suddenly appearing conductive bridges and their relation to the synchrony state of the oscillator ensemble will be discussed.

Discovery of a Peptoid-Based Nanoparticle Platform for Therapeutic mRNA Delivery via Diverse Library Clustering and Structural Parametrization.

Nanoparticle-mediated mRNA delivery has emerged as a promising therapeutic modality, but its growth is still limited by the discovery and optimization of effective and well-tolerated delivery strategies. Lipid nanoparticles containing charged or ionizable lipids are an emerging standard for in vivo mRNA delivery, so creating facile, tunable strategies to synthesize these key lipid-like molecules is essential to advance the field. Here, we generate a library of N-substituted glycine oligomers, peptoids, and undertake a multistage down-selection process to identify lead candidate peptoids as the ionizable component in our Nutshell nanoparticle platform. First, we identify a promising peptoid structural motif by clustering a library of >200 molecules based on predicted physical properties and evaluate members of each cluster for reporter gene expression in vivo. Then, the lead peptoid motif is optimized using design of experiments methodology to explore variations on the charged and lipophilic portions of the peptoid, facilitating the discovery of trends between structural elements and nanoparticle properties. We further demonstrate that peptoid-based Nutshells leads to expression of therapeutically relevant levels of an anti-respiratory syncytial virus antibody in mice with minimal tolerability concerns or induced immune responses compared to benchmark ionizable lipid, DLin-MC3-DMA. Through this work, we present peptoid-based nanoparticles as a tunable delivery platform that can be optimized toward a range of therapeutic programs.

Impact of surface-active ionic solutions on the structure and function of laccase from trametes versicolor: Insights from molecular dynamics simulations

Many protein-ionic liquid investigations have examined laccase interactions. Laccases are a class of poly-copper oxidoreductases that retain significant biotechnological relevance owing to their notable oxidative capabilities and their application in the elimination of synthetic dyes, phenolic compounds, insecticides, and various other substances. This study investigates the impact of surface active ionic liquids (SAILs), namely, decyltrimethylammonium bromide [N10111][Br] and 1-decyl-3-methylimidazolium chloride [C10mim][Cl] as cationic surfactant ionic liquids and cholinium decanoate [Chl][Dec], an anionic surfactant ionic liquid, on the structure and function of laccase from the fungus Trametes versicolor (TvL) by the molecular dynamics (MD) simulation method. In summary, this study showed that laccase solvent-accessible surface area increased in the ionic liquid [Chl][Dec] while it decreased in the other two ionic liquids. Interestingly, [Chl][Dec] ionic liquid components formed hydrogen bonds with laccase, while [N10111][Br] and [C10mim][Cl] components were unable to form hydrogen bonds with laccase. The quantity of hydrogen bonds formed between water molecules and the enzyme was also diminished in the presence of [Chl][Dec] in comparison to the other two ionic liquids. especially at a concentration of 250 mM. In 250 mM concentrations of [N10111][Br] and [C10mim][Cl], clusters of long-chain cations are likely to form near the copper T1 site. However, even at low [Chl][Dec] concentrations, long [Dec]- chains were observed to penetrate the enzyme near the copper T1 site, and at 250 mM [Chl][Dec], a large cluster of anions occupied the opening of the active site. The results of the analysis also show that the interaction between the [Dec]- anion and the enzyme is stronger than the interaction between [N10111]+ and [C10mim]+ with laccase; in addition, the [Dec]- anion, compared to [Br]- and [Cl]- has a much greater tendency to bind with the enzyme residues.