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Parents' perception of cyberbullying of their children inside Saudi Persia.
DNA conformation, in particular its supercoiling, plays an important structural and functional role in gene accessibility as well as in DNA condensation. Enzyme driven changes of DNA plasmids between their linear, circular and supercoiled conformations control the level of condensation and DNA distal-site interactions. Much effort has been made to quantify the branched supercoiled state of DNA to understand its ubiquitous contribution to many biological functions, such as packaging, transcription, replication etc. Nanopore technology has proven to be an excellent label-free single-molecule method to investigate the conformations of the translocating DNA in terms of the current pulse readout. In this paper, we present a comprehensive study to detect different branched-supercoils on individual plasmid DNA molecules. Using a detailed event charge deficit (ECD) analysis of the translocating molecules, we reveal, for the first time, the distributions in size and the position of the plectoneme branches on the supercoiled plasmid. Additionally, this analysis also gives an independent measure of the effective nanopore length. Finally, we use our nanopore platform for measurement of enzyme-dependent linearization of these branched-supercoiled plasmids. By simultaneous measurement of both single-molecule DNA supercoiled conformations and enzyme-dependent bulk conformational changes, we establish nanopore sensing as a promising platform for an in-depth understanding of the structural landscapes of supercoiled DNA to decipher its functional role in different biological processes.The outer blood-retinal barrier (oBRB) tightly controls the transport processes between the neural tissue of the retina and the underlying blood vessel network. The barrier is formed by the retinal pigment epithelium (RPE), its basal membrane and the underlying choroidal capillary bed. Realistic three-dimensional cell culture based models of the oBRB are needed to study mechanisms and potential treatments of visual disorders such as age-related macular degeneration that result from dysfunction of the barrier tissue. Ideally, such models should also include clinically relevant read-outs to enable translation of experimental findings in the context of pathophysiology. Here, we report a microfluidic organ-on-a-chip model of the oBRB that contains a monolayer of human immortalized RPE and a microvessel of human endothelial cells, separated by a semi-permeable membrane. Confluent monolayers of both cell types were confirmed by fluorescence microscopy. The three-dimensional vascular structures within the chip were imaged by optical coherence tomography a medical imaging technique, which is routinely applied in ophthalmology. Differences in diameters and vessel density could be readily detected. Upon inducing oxidative stress by treating with hydrogen peroxide (H2O2), a dose dependent increase in barrier permeability was observed by using a dynamic assay for fluorescence tracing, analogous to the clinically used fluorescence angiography. check details This organ-on-a-chip of the oBRB will allow future studies of complex disease mechanisms and treatments for visual disorders using clinically relevant endpoints in vitro.The effect of para-substitution upon the structural and electronic properties of a series of m-terphenyl lithium complexes [R-Ar#-Li]2 (R = t-Bu 1, SiMe32, H 3, Cl 4, CF35; where R-Ar# = 2,6-2,6-Xyl2-4-R-C6H2 and 2,6-Xyl = 2,6-Me2C6H3) has been investigated. X-ray crystallography reveals the complexes to be structurally similar, with little variation in C-M-C bond lengths and angles across the series. However, in-depth NMR spectroscopic studies reveal notable electronic differences, showing a linear correlation between the 7Li1H NMR chemical shifts of the para-substituted complexes and their Hammett constants. The flanking methyl protons exhibit a similar electronic shift in the 1H NMR spectra, which has been rationalised by the presence of through-space LiH interactions, as evidenced by two-dimensional 7Li-1H heteronuclear Overhauser spectroscopy (HOESY). In both cases, electron-withdrawing substituents are found to cause an upfield peak shift. A computational analysis is employed to account for these trends.This paper presents a thorough quantum investigation of the optical properties of twelve transition metal complexes using state of the art (TD)DFT computations. The studied molecules are two Pt-based and ten Ir-based complexes. Geometrical parameters, absorption and emission spectra are directly compared to available experimental data. Phosphorescence spectra have been computed within the Adiabatic Hessian (AH) method which takes into account mode mixing and a proper description of both ground and excited states potential energy surfaces (frequency calculations). For each compound, three methods have been considered to obtain the relaxed triplet excited state supposedly involved in the phosphorescence process, i.e. unrestricted DFT, TDDFT and its Tamm-Dancoff approximation (TDA). In overall, unrestricted DFT and TDA overperform TDDFT for the investigated complexes especially when an Ir centre is present. The AH model demonstrates its good capability to reproduce accurately phosphorescence spectra. Finally, simulation and experimental data are represented over a CIE chromaticity horseshoe.Colloidal particles have been extensively used to comprehend the main principles governing liquid-crystal nucleation. Multiple mechanisms and frameworks have been proposed, through either experiments or computational approaches, to rationalise the ubiquitous formation of colloidal crystals. In this work, we elucidate the nucleation scenario behind the crystallization of oppositely charged colloids. By performing molecular dynamics simulations of colloidal electrolytes in combination with the Seeding technique, we evaluate the fundamental factors, such as the nucleation rate, free energy barrier, surface tension and kinetic pre-factor, that determine the liquid-to-solid transition of several crystalline polymorphs. Our results show that at a high packing fraction, there is a cross-over between the nucleation of the CsCl structure and that of a substitutionally disordered fcc phase, despite the CuAu crystal being the most stable phase. We demonstrate that the crucial factor in determining which phase nucleates the fastest is the free energy cost of the cluster formation rather than their kinetic ability to grow from the liquid. While at a low packing fraction, the stable phase, CsCl, is the one that nucleates and subsequently grows, we show how at moderate and high packing fractions, a disordered fcc phase subsequently grows regardless of the nature of the nucleating phase, termed parasitic crystallization. Taken together, our results provide a panoramic perspective of the complex nucleation scenario of oppositely charged colloids at moderate temperature and rationalise the different thermodynamic and kinetic aspects behind it.We present trace gas vertical profiles observed by instruments on the NASA DC-8 and at a ground site during the Korea-US air quality study (KORUS) field campaign in May to June 2016. We focus on the region near the Seoul metropolitan area and its surroundings where both anthropogenic and natural emission sources play an important role in local photochemistry. Integrating ground and airborne observations is the major research goal of many atmospheric chemistry field campaigns. Although airborne platforms typically aim to sample from near surface to the free troposphere, it is difficult to fly very close to the surface especially in environments with complex terrain or a populated area. A detailed analysis integrating ground and airborne observations associated with specific concentration footprints indicates that reactive trace gases are quickly oxidized below an altitude of 700 m. The total OH reactivity profile has a rapid decay in the lower part of troposphere from surface to the lowest altitude (700 m) sampled by the NASA DC-8. The decay rate is close to that of very reactive biogenic volatile organic compounds such as monoterpenes. Therefore, we argue that photochemical processes in the bottom of the boundary layer, below the typical altitude of aircraft sampling, should be thoroughly investigated to properly assess ozone and secondary aerosol formation.Reversibly programmable liquid crystal elastomer microparticles (LCEMPs), formed as a covalent adaptable network (CAN), with an average diameter of 7 μm ± 2 μm, were synthesized via a thiol-Michael dispersion polymerization. The particles were programmed to a prolate shape via a photoinitiated addition-fragmentation chain-transfer (AFT) exchange reaction by activating the AFT after undergoing compression. Due to the thermotropic nature of the AFT-LCEMPs, shape switching was driven by heating the particles above their nematic-isotropic phase transition temperature (TNI). The programmed particles subsequently displayed cyclable two-way shape switching from prolate to spherical when at low or high temperatures, respectively. Furthermore, the shape programming is reversible, and a second programming step was done to erase the prolate shape by initiating AFT at high temperature while the particles were in their spherical shape. Upon cooling, the particles remained spherical until additional programming steps were taken. Particles were also programmed to maintain a permanent oblate shape. Additionally, the particle surface was programmed with a diffraction grating, demonstrating programmable complex surface topography via AFT activation.Free-standing Pt-Ni nanowires were fabricated by a one-pot solvothermal method. Nanowires with an optimal Pt/Ni ratio of 1.86 exhibited a high activity and a 100% H2 selectivity for hydrous hydrazine decomposition at mild temperatures, which are comparable to the levels of supported catalysts. Our study reveals for the first time that basic support is not a prerequisite for achieving favorable catalytic performance and provides a renewed perspective for the design of advanced catalysts for on-demand H2 generation from hydrous hydrazine.A hydrophosphination reaction of alkenes with triphenylphosphonium triflate under photocatalytic conditions is described. The reaction is promoted by naphthalene-fused N-acylbenzimidazole and is believed to proceed through intermediate formation of a phosphinyl radical cation. The resulting phosphonium salts are directly involved in the Wittig reaction leading to homologated alkenes.First-principles calculations were performed to study the electrochemical performance of M2TiC2 (M = Cr or Mo) and M2TiC2Tx (T = O, F or OH) used as anode materials for sodium ion batteries (SIBs). The O functionalized MXenes (Cr2TiC2O2 and Mo2TiC2O2) are found to be more stable than F and OH terminated systems. The diffusion performance of sodium in MXene materials is mainly affected by the functional groups. The lowest diffusion barrier of functionalized MXenes is about one order larger in magnitude than that of bare MXenes. Although the introduction of O-groups hinders the diffusion of sodium, it can greatly improve the theoretical storage capacities. Meanwhile, the diffusion paths and diffusion energy barriers of Na are affected by Na concentration effects, while the interactions between terminations have little effect. Furthermore, multiple layers of sodium atoms are found to be adsorbed between the layers of M2TiC2O2, thus significantly increasing the theoretical capacities. The theoretical sodium storage capacities of M2TiC2O2 monolayers reach 515.
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