Resolving the Mechanism of Acoustic Plasmon Instability in Graphene Doped by Alkali Metals

Graphene doped by alkali atoms (ACx) supports two heavily populated bands (π and σ) crossing the Fermi level, which enables the formation of two intense two-dimensional plasmons: the Dirac plasmon (DP) and the acoustic plasmon (AP). Although the mechanism of the formation of these plasmons in electrostatically biased graphene or at noble metal surfaces is well known, the mechanism of their formation in alkali-doped graphenes is still not completely understood. We shall demonstrate that two isoelectronic systems, KC8 and CsC8, support substantially different plasmonic spectra: the KC8 supports a sharp DP and a well-defined AP, while the CsC8 supports a broad DP and does not support an AP at all. We shall demonstrate that the AP in an ACx is not, as previously believed, just a consequence of the interplay of the π and σ intraband transitions, but a very subtle interplay between these transitions and the background screening, caused by the out-of-plane interband C(π)→A(σ) transitions.     

Prediction of Strong Transversal s(TE) Exciton–Polaritons in C60 Thin Crystalline Films

If an exciton and a photon can change each other’s properties, indicating that the regime of their strong bond is achieved, it usually happens in standard microcavity devices, where the large overlap between the ’confined’ cavity photons and the 2D excitons enable the hybridization and the band gap opening in the parabolic photonic branch (as clear evidence of the strong exciton–photon coupling). Here, we show that the strong light–matter coupling can occur beyond the microcavity device setup, i.e., between the ’free’ s(TE) photons and excitons. The s(TE) exciton–polariton is a polarization mode, which (contrary to the p(TM) mode) appears only as a coexistence of a photon and an exciton, i.e., it vanishes in the non-retarded limit (c→∞). We show that a thin fullerene C60 crystalline film (consisting of N C60 single layers) deposited on an Al2O3 dielectric surface supports strong evanescent s(TE)-polarized exciton–polariton. The calculated Rabi splitting is more than Ω=500 meV for N=10, with a tendency to increase with N, indicating a very strong photonic character of the exciton–polariton.     

Optimizing Chain Topology of Bottle Brush Copolymer for Promoting the Disorder-to-Order Transition

The order-disorder transitions (ODT) of core-shell bottle brush copolymer and its structural isomers were investigated by dissipative particle dynamics simulations and theoretically by random phase approximation. Introducing a chain topology parameter λ which parametrizes linking points between M diblock chains each with N monomers, the degree of incompatibility at ODT ((χN)ODT; χ being the Flory–Huggins interaction parameter between constituent monomers) was predicted as a function of chain topology parameter (λ) and the number of linked diblock chains per bottle brush copolymer (M). It was found that there exists an optimal chain topology about λ at which (χN)ODT gets a minimum while the domain spacing remains nearly unchanged. The prediction provides a theoretical guideline for designing an optimal copolymer architecture capable of forming sub-10 nm periodic structures even with non-high χ components.     

New Light on an Old Story: Breaking Kasha’s Rule in Phosphorescence Mechanism of Organic Boron Compounds and Molecule Design

In this work, the phosphorescence mechanism of (E)-3-(((4-nitrophenyl)imino)methyl)-2H-thiochroman-4-olate-BF2 compound (S-BF2) is investigated theoretically. The phosphorescence of S-BF2 has been reassigned to the second triplet state (T2) by the density matrix renormalization group (DMRG) method combined with the multi-configurational pair density functional theory (MCPDFT) to approach the limit of theoretical accuracy. The calculated radiative and non-radiative rate constants support the breakdown of Kasha’s rule further. Our conclusion contradicts previous reports that phosphorescence comes from the first triplet state (T1). Based on the revised phosphorescence mechanism, we have purposefully designed some novel compounds in theory to enhance the phosphorescence efficiency from T2 by replacing substitute groups in S-BF2. Overall, both S-BF2 and newly designed high-efficiency molecules exhibit anti-Kasha T2 phosphorescence instead of the conventional T1 emission. This work provides a useful guidance for future design of high-efficiency green-emitting phosphors.     

Shear Stress Enhances the Paracrine-Mediated Immunoregulatory Function of Human Periodontal Ligament Stem Cells via the ERK Signalling Pathway

Relevant immunomodulatory effects have been proposed following allogeneic cell-based therapy with human periodontal ligament stem cells (hPDLSCs). This study aimed to examine the influence of shear stress on the immunosuppressive capacity of hPDLSCs. Cells were subjected to shear stress at different magnitudes (0.5, 5 and 10 dyn/cm2). The expression of immunosuppressive markers was evaluated in shear stress-induced hPDLSCs using qRT-PCR, western blot, enzyme activity and enzyme-linked immunosorbent assays. The effects of a shear stress-derived condition medium (SS-CM) on T cell proliferation were examined using a resazurin assay. Treg differentiation was investigated using qRT-PCR and flow cytometry analysis. Our results revealed that shear stress increased mRNA expression of IDO and COX2 but not TGF-β1 and IFN-γ. IDO activity, kynurenine and active TGF-β1 increased in SS-CM when compared to the non-shear stress-derived conditioned medium (CTL-CM). The amount of kynurenine in SS-CM was reduced in the presence of cycloheximide and ERK inhibitor. Subsequently, T cell proliferation decreased in SS-CM compared to CTL-CM. Treg differentiation was promoted in SS-CM, indicated by FOXP3, IL-10 expression and CD4+CD25hiCD127lo/− subpopulation. In conclusion, shear stress promotes kynurenine production through ERK signalling in hPDLSC, leading to the inhibition of T cell proliferation and the promotion of Treg cell differentiation.     

Spontaneous and Ionizing Radiation-Induced Aggregation of Human Serum Albumin: Dityrosine as a Fluorescent Probe

The use of spectroscopic techniques has shown that human serum albumin (HSA) undergoes reversible self-aggregation through protein–protein interactions. It ensures the subsequent overlapping of electron clouds along with the stiffening of the conformation of the interpenetrating network of amino acids of adjacent HSA molecules. The HSA oxidation process related to the transfer of one electron was investigated by pulse radiolysis and photochemical methods. It has been shown that the irradiation of HSA solutions under oxidative stress conditions results in the formation of stable protein aggregates. The HSA aggregates induced by ionizing radiation are characterized by specific fluorescence compared to the emission of non-irradiated solutions. We assume that HSA dimers are mainly responsible for the new emission. Dityrosine produced by the intermolecular recombination of protein tyrosine radicals as a result of radiolysis of an aqueous solution of the protein is the main cause of HSA aggregation by cross-linking. Analysis of the oxidation process of HSA confirmed that the reaction of mild oxidants (Br2•−, N3•, SO4•−) with albumin leads to the formation of covalent bonds between tyrosine residues. In the case of ^•OH radicals and partly, Cl2•−, species other than DT are formed. The light emission of this species is similar to the emission of self-associated HSA.     

Novel All-Nitrogen Molecular Crystals Composed of Tetragonal N4 Molecules

A computational study promises insight into molecular crystals consisting of the tetrahedral form of N4 molecules (Td-N4). Here, our efforts are focused on theoretically predicting the existence of the molecular crystals consisting of Td-N4 molecules. On the basis of the first principles of Born–Oppenheimer molecular dynamics under constant temperature and pressure, and geometry optimizations under hydrostatic pressures without any constrained parameters, molecular crystals consisting of Td-N4 molecules were confirmed to be dynamically and thermally metastable. Our analysis shows that, with high detonation performance and high stability, these Td-N4 molecular crystals can indeed be potential candidates as high-energy density explosives.     

Electron-Capture Cross Sections of Ground-State O2+ Recoil Ions in Slow Collisions with H2 and O2

We report the measured total charge-transfer (electron-capture) cross sections for the ground state O2+ (X2Πg) ions with H₂ and O₂ molecular gases in the collision energy range between 0.50 and 2 keV. The time-of-flight technique has been used to measure the fast neutral products from O2+ charge transfer reactions. The analyzed process has cross sections that continue to increase slowly, as a function of incident energy. Measured cross sections for O2++H2, O₂ systems are compared with previously available experimental and theoretical results in the literature.     

Interactions between S100A9 and Alpha-Synuclein: Insight from NMR Spectroscopy

S100A9 is a pro-inflammatory protein that co-aggregates with other proteins in amyloid fibril plaques. S100A9 can influence the aggregation kinetics and amyloid fibril structure of alpha-synuclein (α-syn), which is involved in Parkinson’s disease. Currently, there are limited data regarding their cross-interaction and how it influences the aggregation process. In this work, we analyzed this interaction using solution 19F and 2D ¹⁵N–¹H HSQC NMR spectroscopy and studied the aggregation properties of these two proteins. Here, we show that α-syn interacts with S100A9 at specific regions, which are also essential in the first step of aggregation. We also demonstrate that the 4-fluorophenylalanine label in alpha-synuclein is a sensitive probe to study interaction and aggregation using 19F NMR spectroscopy.     

Spin State Switching in Heptauthrene Nanostructure by Electric Field: Computational Study

Recent experimental studies proved the presence of the triplet spin state in atomically precise heptauthrene nanostructure of nanographene type (composed of two interconnected triangles with zigzag edge). In the paper, we report the computational study predicting the possibility of controlling this spin state with an external in-plane electric field by causing the spin switching. We construct and discuss the ground state magnetic phase diagram involving S=1 (triplet) state, S=0 antiferromagnetic state and non-magnetic state and predict the switching possibility with the critical electric field of the order of 0.1 V/Å. We discuss the spin distribution across the nanostructure, finding its concentration along the longest zigzag edge. To model our system of interest, we use the mean-field Hubbard Hamiltonian, taking into account the in-plane external electric field as well as the in-plane magnetic field (in a form of the exchange field from the substrate). We also assess the effect of uniaxial strain on the magnetic phase diagram.     

Theoretical Design of a Janus-Nanoparticle-Based Sandwich Assay for Nucleic Acids

Nanoparticles exhibit diverse self-assembly attributes and are expected to be applicable under unique settings. For instance, biomolecules can be sandwiched between dimer nanoparticles and detected by surface-enhanced Raman scattering. Controlling the gap between extremely close dimers and stably capturing the target molecule in the gap are crucial aspects of this strategy. Therefore, polymer-tethered nanoparticles (PTNPs), which show promise as high-performance materials that exhibit the attractive features of both NPs and polymers, were targeted in this study to achieve stable biomolecule sensing. Using coarse-grained molecular dynamics simulations, the dependence of the PTNP interactions on the length of the grafted polymer, graft density, and coverage ratio of a hydrophobic tether were examined. The results indicated that the smaller the tether length and graft density, the smaller was the distance between the PTNP surfaces (Rsurf). In contrast, Rsurf decreased as the coverage ratio of the hydrophobic surface (ϕ) increased. The sandwiching probability of the sensing target increased in proportion to the coverage ratio. At high ϕ values, the PTNPs aggregated into three or more particles, which hindered their sensing attributes. These results provide fundamental insight into the sensing applications of NPs and demonstrate the usefulness of PTNPs in sensing biomolecules.     

3D Printed Cobalt-Chromium-Molybdenum Porous Superalloy with Superior Antiviral Activity

COVID-19 pandemic and associated supply-chain disruptions emphasise the requirement for antimicrobial materials for on-demand manufacturing. Besides aerosol transmission, SARS-CoV-2 is also propagated through contact with virus-contaminated surfaces. As such, the development of effective biofunctional materials that can inactivate SARS-CoV-2 is critical for pandemic preparedness. Such materials will enable the rational development of antiviral devices with prolonged serviceability, reducing the environmental burden of disposable alternatives. This research reveals the novel use of Laser Powder Bed Fusion (LPBF) to 3D print porous Cobalt-Chromium-Molybdenum (Co-Cr-Mo) superalloy with potent antiviral activity (100% viral inactivation in 30 min). The porous material was rationally conceived using a multi-objective surrogate model featuring track thickness (tt) and pore diameter (ϕd) as responses. The regression analysis found the most significant parameters for Co-Cr-Mo track formation to be the interaction effects of scanning rate (Vs) and laser power (Pl) in the order PlVs>Vs>Pl. Contrastively, the pore diameter was found to be primarily driven by the hatch spacing (Sh). The study is the first to demonstrate the superior antiviral properties of 3D printed Co-Cr-Mo superalloy against an enveloped virus used as biosafe viral model of SARS-CoV-2. The material significantly outperforms the viral inactivation time of other broadly used antiviral metals such as copper and silver, as the material’s viral inactivation time was from 5 h to 30 min. As such, the study goes beyond the current state-of-the-art in antiviral alloys to provide extra protection to combat the SARS-CoV-2 viral spread. The evolving nature of the COVID-19 pandemic brings new and unpredictable challenges where on-demand 3D printing of antiviral materials can achieve rapid solutions while reducing the environmental impact of disposable devices.     

Dynamic Changes in Reactive Oxygen Species in the Shoot Apex Contribute to Stem Cell Death in Arabidopsis thaliana

In monocarpic plants, stem cells are fated to die. However, the potential mechanism of stem cell death has remained elusive. Here, we reveal that the levels of two forms of reactive oxygen species (ROS), superoxide anion free radical (O2·−) and hydrogen peroxide (H₂O₂), show dynamic changes in the shoot apex during the plant life cycle of Arabidopsis thaliana. We found that the level of O2·− decreased and disappeared at four weeks after bolting (WAB), while H₂O₂ appeared at 3 WAB and showed a burst at 5 WAB. The timing of dynamic changes in O2·− and H₂O₂ was delayed for approximately three weeks in clv3-2, which has a longer lifespan. Moreover, exogenous application of H₂O₂ inhibited the expression of the stem cell determinant WUSCHEL (WUS) and promoted the expression of the developmentally programmed cell death (dPCD) marker gene ORESARA 1 (ORE1). These results indicate that H₂O₂ triggers an important signal inducing dPCD in stem cells. Given that O2·− plays roles in maintaining WUS expression and stem cell activity, we speculate that the dynamic shift from O2·− to H₂O₂ in the shoot apex results in stem cell death. Our findings provide novel insights for understanding ROS-mediated regulation during plant stem cell death.     

Indium-doped ZnO nanowires with infrequent growth orientation,rough surfaces and low-density surface traps

Indium-doped ZnO nanowires have been prepared by vapor transport deposition. With increasing In content, the growth orientation of the nanowires switches from [101_0] to infrequent [022_3] and the surface becomes rough. No surface-related exciton emission is observed in these nanowires. The results indicate that large surface-to-volume ratio, high free electron concentration, and low density of surface traps can be achieved simultaneously in ZnO nanowires via In doping. These unique properties make In-doped ZnO nanowire a potential material for photocatalysis application, which is demonstrated by the enhanced photocatalytic degradation of Rhodamine B.     

Time-Dependent Image Restoration of Low-SNR Live-Cell Ca2 Fluorescence Microscopy Data

Live-cell Ca2+ fluorescence microscopy is a cornerstone of cellular signaling analysis and imaging. The demand for high spatial and temporal imaging resolution is, however, intrinsically linked to a low signal-to-noise ratio (SNR) of the acquired spatio-temporal image data, which impedes on the subsequent image analysis. Advanced deconvolution and image restoration algorithms can partly mitigate the corresponding problems but are usually defined only for static images. Frame-by-frame application to spatio-temporal image data neglects inter-frame contextual relationships and temporal consistency of the imaged biological processes. Here, we propose a variational approach to time-dependent image restoration built on entropy-based regularization specifically suited to process low- and lowest-SNR fluorescence microscopy data. The advantage of the presented approach is demonstrated by means of four datasets: synthetic data for in-depth evaluation of the algorithm behavior; two datasets acquired for analysis of initial Ca2+ microdomains in T-cells; finally, to illustrate the transferability of the methodical concept to different applications, one dataset depicting spontaneous Ca2+ signaling in jGCaMP7b-expressing astrocytes. To foster re-use and reproducibility, the source code is made publicly available.     

Polarized photoreflectance and photoluminescence spectroscopy of InGaAs/GaAs quantum rods grown with As2 and As4 sources

We report photoreflectance (PR) and photoluminescence (PL) investigations of the electronic and polarization properties of different aspect ratio (height/diameter) InGaAs quantum rods (QRs) embedded in InGaAs quantum wells (QWs). These nanostructures were grown by molecular beam epitaxy using As₂or As₄sources. The impact of the As source on the spectral and polarization features of the QR- and QW-related interband transitions was investigated and explained in terms of the carrier confinement effects caused by variation of composition contrast between the QR material and the surrounding well. Polarized PR and PL measurements reveal that the polarization has a preferential direction along the [11¯0] crystal axis with a large optical anisotropy of about 60% in the (001) plane for high aspect ratio (4.1:1) InGaAs QRs. As a result, in PL spectra, the transverse magnetic mode dominated (11¯0)-cleaved surfaces (TM_[001]>TE_[110]), whereas the transverse electric mode prevailed for (110)-cleaved surfaces (TM[001]<TE[11¯0]). This strong optical anisotropy in the (001) plane is interpreted in terms of the hole wavefunction orientation along the [11¯0] direction for high aspect ratio QRs.     

Simulations of Promising Indolizidine—α6-β2 Nicotinic Acetylcholine Receptor Complexes

Smoking-cessation drugs bind many off-target nicotinic acetylcholine receptors (nAChRs) and cause severe side effects if they are based on nicotine. New drugs that bind only those receptors, such as α6β2* nAChR, implicated in nicotine addiction would avoid the off-target binding. Indolizidine (-)-237D (IND (-)-237D), a bicyclic alkaloid, has been shown to block α6β2* containing nAChRs and functionally inhibit the nicotine-evoked dopamine release. To improve the affinity of indolizidine (-)-237D for α6β2*, we built a library of 2226 analogs. We screened virtually the library against a homology model of α6β2 nAChR that we derived from the recent crystal structure of α4β2 nAChR. We also screened the crystal structure of α4β2 nAChR as a control on specificity. We ranked the compounds based on their predicted free energy of binding. We selected the top eight compounds bound in their best pose and subjected the complexes to 100 ns molecular dynamics simulations to assess the stability of the complexes. All eight analogs formed stable complexes for the duration of the simulations. The results from this work highlight nine distinct analogs of IND (-)-237D with high affinity towards α6β2* nAChR. These leads can be synthesized and tested in in vitro and in vivo studies as lead candidates for drugs to treat nicotine addiction.     

Hydrophilic and Hydrophobic Effects on the Structure and Themodynamic Properties of Confined Water: Water in Solutions

NMR spectroscopy is used in the temperature range 180–350 K to study the local order and transport properties of pure liquid water (bulk and confined) and its solutions with glycerol and methanol at different molar fractions. We focused our interest on the hydrophobic effects (HE), i.e., the competition between hydrophilic and hydrophobic interactions. Nowadays, compared to hydrophilicity, little is known about hydrophobicity. Therefore, the main purpose of this study is to gain new information about hydrophobicity. As the liquid water properties are dominated by polymorphism (two coexisting liquid phases of high and low density) due to hydrogen bond interactions (HB), creating (especially in the supercooled regime) the tetrahedral networking, we focused our interest to the HE of these structures. We measured the relaxation times (T1 and T2) and the self-diffusion (DS). From these times, we took advantage of the NMR property to follow the behaviors of each molecular component (the hydrophilic and hydrophobic groups) separately. In contrast, DS is studied in terms of the Adam–Gibbs model by obtaining the configurational entropy (Sconf) and the specific heat contributions (CP,conf). We find that, for the HE, all of the studied quantities behave differently. For water–glycerol, the HB interaction is dominant for all conditions; water–methanol, two different T-regions above and below 265 K are observable, dominated by hydrophobicity and hydrophilicity, respectively. Below this temperature, where the LDL phase and the HB network develops and grows, with the times and CP,conf change behaviors leading to maxima and minima. Above it, the HB becomes weak and less stable, the HDL dominates, and hydrophobicity determines the solution.     

Non-Covalent Forces in Naphthazarin—Cooperativity or Competition in the Light of Theoretical Approaches

Non-covalent interactions responsible for molecular features and self-assembly in Naphthazarin C polymorph were investigated on the basis of diverse theoretical approaches: Density Functional Theory (DFT), Diffusion Quantum Monte Carlo (DQMC), Symmetry-Adapted Perturbation Theory (SAPT) and Car-Parrinello Molecular Dynamics (CPMD). The proton reaction paths in the intramolecular hydrogen bridges were studied. Two potential energy minima were found indicating that the proton transfer phenomena occur in the electronic ground state. Diffusion Quantum Monte Carlo (DQMC) and other levels of theory including Coupled Cluster (CC) employment enabled an accurate inspection of Potential Energy Surface (PES) and revealed the energy barrier for the proton transfer. The structure and reactivity evolution associated with the proton transfer were investigated using Harmonic Oscillator Model of Aromaticity - HOMA index, Fukui functions and Atoms In Molecules (AIM) theory. The energy partitioning in the studied dimers was carried out based on Symmetry-Adapted Perturbation Theory (SAPT) indicating that dispersive forces are dominant in the structure stabilization. The CPMD simulations were performed at 60 K and 300 K in vacuo and in the crystalline phase. The temperature influence on the bridged protons dynamics was studied and showed that the proton transfer phenomena were not observed at 60 K, but the frequent events were noticed at 300 K in both studied phases. The spectroscopic signatures derived from the CPMD were computed using Fourier transformation of autocorrelation function of atomic velocity for the whole molecule and bridged protons. The computed gas-phase IR spectra showed two regions with OH absorption that covers frequencies from 2500 cm−1 to 2800 cm−1 at 60 K and from 2350 cm−1 to 3250 cm−1 at 300 K for both bridged protons. In comparison, the solid state computed IR spectra revealed the environmental influence on the vibrational features. For each of them absorption regions were found between 2700–3100 cm−1 and 2400–2850 cm−1 at 60 K and 2300–3300 cm−1 and 2300–3200 cm−1 at 300 K respectively. Therefore, the CPMD study results indicated that there is a cooperation of intramolecular hydrogen bonds in Naphthazarin molecule.