Notes

Photo- along with thermochromic and adsorption components associated with permeable control polymers determined by bipyridinium carboxylate ligands.
This paper reports on the hydrothermal synthesis of a novel 2D material, magnesium silicate hydroxide/carbon (MSH/C) core-shell nanoplate, in a graphite-MgO-SiO2-NaOH system at 300 °C and 12 MPa for 48 h. Its significant potentials as an antiwear additive in lubricant oil were subsequently demonstrated. The 2D nanoplates consist of an MSH core and a 1-6 nm thick sp2-hybridized carbon shell with a layer spacing of 0.34 nm. In typical four-ball tests at a maximum Hertzian pressure of 3.4 GPa, the MSH/C core-shell nanoplates nearly eliminated wear, whether suspended in poly alpha-olefin oil or fully formulated lubricating oil, and the corresponding volume wear rates were reduced by 96.33% and 72%, respectively. The excellent antiwear performance was ascribed to the formation of a tribofilm consisting of diffusedly distributed Fe3O4 nanocrystals and carbon- and/or SiO x -containing amorphous structures.Hydrogen-bonded structures and their lifetimes in ionic liquids (ILs) are governed by the subtle balance between Coulomb interactions, hydrogen bonding, and dispersion forces. Despite the dominant Coulomb interaction, local and directional hydrogen bonds (HBs) can play an important role in the behavior of ILs. Compared to water, the archetype of hydrogen-bonded liquids, ILs have larger constituents and higher viscosities but are typically lacking a three-dimensional HB network. Hydroxyl-functionalized ionic liquids are even more special regular HBs between cations and anions (ca) are accompanied by HBs between pairs of cations (cc). Recently, infrared (IR) measurements have suggested that the (cc) HBs are even stronger than their (ca) counterparts and their strength can be controlled via the hydroxyalkyl chain length. In this paper, we show by means of molecular dynamics (MD) simulations that the presence of HBs has a profound effect on the molecular mobility of the ions. We investigate the kinetic mechanism of hydrogen bonding in ILs and show that the lifetimes and hence the stability of (cc) HBs increase with the chain length, making them more stable than the respective (ca) HBs. The observed HB equilibrium can explain the peculiar chain length dependence of the relative molecular mobilities of the ions by a direct comparison between hydroxyl-functionalized ILs with their nonfunctionalized counterparts.It is widely recognized that solvation is one of the major factors determining structure and functionality of proteins and long peptides, however it is a formidable challenge to address it both experimentally and computationally. For this reason, simple peptides are used to study fundamental aspects of solvation. It is well established that alcohols can change the peptide conformation and tuning of the alcohol content in solution can dramatically affect folding and, as a consequence, the function of the peptide. In this work, we focus on the leucine and lysine based LKα14 peptide designed to adopt an α-helical conformation at an apolar-polar interface. We investigate LKα14 peptide's bulk and interfacial behavior in water/ethanol mixtures combining a suite of experimental techniques (namely, circular dichroism and nuclear magnetic resonance spectroscopy for the bulk solution, surface pressure measurements and vibrational sum frequency generation spectroscopy for the air-solution interface) with molecular dynamics simulations. We observe that ethanol highly affects both the peptide location and conformation. At low ethanol content LKα14 lacks a clear secondary structure in bulk and shows a clear preference to reside at the air-solution interface. When the ethanol content in solution increases, the peptide's interfacial affinity is markedly reduced and the peptide approaches a stable α-helical conformation in bulk facilitated by the amphiphilic nature of the ethanol molecules.A heterojunction is an essential strategy for multispectral energy-conservation photodetection for its ability to separate photogenerated electron-hole pairs and tune the absorption edge by selecting semiconductors with appropriate bandgaps. A broadband ultraviolet (200-410 nm) self-powered photodetector is constructed on the exfoliated β-Ga2O3/CuI core-shell microwire heterostructure. Benefiting from the photovoltaic and photoconductive effects, our device performs an excellent ultraviolet (UV) discriminability with a UVC/visible rejection ratio (R225/R600) of 8.8 × 103 and a UVA/visible rejection ratio (R400/R600) of 2.7 × 102, and a self-powered photodetection with a responsivity of 8.46 mA/W, a detectivity of 7.75 × 1011 Jones, an on/off switching ratio of 4.0 × 103, and a raise/decay speed of 97.8/28.9 ms under UVC light. Even without encapsulation, the photodetector keeps a superior stability over ten months. The intrinsically physical insights of the device behaviors are investigated via energy band diagrams, and the charge carrier transfer characteristics of the β-Ga2O3/CuI interface are predicted by first principle calculation.There is an inconsistence on whether a smooth core/shell interface can reduce Auger recombination and suppress photoluminescence (PL) blinking in single colloidal quantum dots (QDs). Here, we investigate the influence of a core/shell interface on PL blinking and biexciton Auger recombination by comparing the single-dot PL spectra of Cd x Zn1-xSe y S1-y/ZnS core/shell QDs with sharp and smooth interfaces. The inconsistence can be clarified when considering different PL blinking mechanisms. For the single QDs showing Auger blinking, a smooth core/shell interface potential can suppress PL blinking through reducing the Auger recombination. In contrast, we find slightly reduced biexciton Auger recombination rates but increased PL blinking activities in the band-edge carrier (BC)-blinking QDs with the smooth core/shell interface. This is because the smooth interface potential cannot reduce the PL blinking caused by the transfer of electrons to the surface states; however, there is potential to increase electron wave function delocalization for reducing the biexciton Auger recombination rate.Long associated with cell death, hydrogen peroxide (H2O2) is now known to perform many physiological roles. Unraveling its biological mechanisms of action requires atomic-level knowledge of its association with proteins and lipids, which we address here. High-level [MP2(full)/6-311++G(3df,3pd)] ab initio calculations reveal skew rotamers as the lowest-energy states of isolated H2O2 (ϕHOOH ∼ 112°) with minimum and maximum electrostatic potentials (kcal/mol) of -24.8 (Vs,min) and 36.5 (Vs,max), respectively. Transition-state, nonpolar trans rotamers (ϕHOOH ∼ 180°) at 1.2 kcal/mol higher in energy are poorer H-bond acceptors (Vs,min = -16.6) than the skew rotamers, while highly polar cis rotamers (ϕHOOH ∼ 0°) at 7.8 kcal/mol are much better H-bond donors (Vs,max = 52.7). Modeling H2O2 association with neutral and charged analogs of protein residues and lipid groups (e.g., ester, phosphate, choline) reveals that skew rotamers (ϕHOOH = 84-122°) are favored in the neutral and cationic complexes, which display gas-phase interaction energies (ECP, kcal/mol) of -1.5 to -18. The neutral and cationic complexes of H2O exhibit a similar range of stabilities (ECP ∼ -1 to -18). However, considerably higher energies (ECP ∼ -14 to -36) are found for the H2O2 complexes of the anionic ligands, which are stabilized by charge-assisted H-bond donation from cis and distorted cis rotamers (ϕHOOH = 0-60°). H2O is a much poorer H-bond donor (Vs,max = 33.4) than cis-H2O2, so its anionic complexes are significantly weaker (ECP ∼ -11 to -20). Thus, by dictating the rotamer preference of H2O2, functional groups in biomolecules can discriminate between H2O2 and H2O. selleck inhibitor Finally, exploiting the present ab initio data, we calibrated and validated our published molecular mechanics model for H2O2 (Orabi, E. A.; English, A. M. J. Chem. Theory Comput. 2018, 14, 2808-2821) to provide an important tool for simulating H2O2 in biology.The instability of glassy solids poses a key limitation to their use in several technological applications. Well-packed organic glasses, prepared by physical vapor deposition (PVD), have drawn attention recently because they can exhibit significantly higher thermal and chemical stability than glasses prepared from more traditional routes. We show here that PVD glasses can also show enhanced resistance to crystallization. By controlling the deposition temperature, resistance toward crystallization can be enhanced by at least a factor of ten in PVD glasses of the model organic semiconductor Alq3 (tris(8-hydroxyquinolinato) aluminum). PVD glasses of Alq3 first transform into a supercooled liquid before crystallizing. By controlling the deposition temperature, we increase the glass → liquid transformation time thereby also increasing the overall time for crystallization. We thus demonstrate a new strategy to stabilize glasses of organic semiconductors against crystallization, which is a common failure mechanism in organic light emitting diode devices.The primary electron donor P700 of the photosystem I (PSI) is a heterodimer consisting of two chlorophyll molecules. A series of electron-transfer events immediately following the initial light excitation leads to a stabilization of the positive charge by its cation radical form, P700+•. The electronic structure of P700+• and, in particular, its asymmetry with respect to the two chlorophyll monomers is of fundamental interest and is not fully understood up to this date. Here, we apply multifrequency X- (9 GHz) and Q-band (35 GHz) hyperfine sublevel correlation (HYSCORE) spectroscopy to investigate the electron spin density distribution in the cation radical P700+• of PSI from a thermophilic cyanobacterium Thermosynechococcus elongatus. Six 14N and two 1H distinct nuclei have been resolved in the HYSCORE spectra and parameters of the corresponding nuclear hyperfine and quadrupolar hyperfine interactions were obtained by combining the analysis of HYSCORE spectral features with direct numerical simulations. Based on a close similarity of the nuclear quadrupole tensor parameters, all of the resolved 14N nuclei were assigned to six out of total eight available pyrrole ring nitrogen atoms (i.e., four in each of the chlorophylls), providing direct evidence of spin density delocalization over the both monomers in the heterodimer. Using the obtained experimental values of the 14N electron-nuclear hyperfine interaction parameters, the upper limit of the electron spin density asymmetry parameter is estimated as RA/Bupper = 7.7 ± 0.5, while a tentative assignment of 14N observed in the HYSCORE spectra yields RB/A = 3.1 ± 0.5.Classical molecular dynamics simulations have been combined with quantum (DFT) calculations of 13C NMR parameters in order to relate the experimental spectrum of the double-helix form of the amylose B-polymorph in highly crystalline conditions not only to its 3D structure but also to the arrangement of atoms in the crystal lattice. Structures obtained from these simulations or from geometry optimization procedures at the DFT level have shown the presence of hydrogen bond networks between sugars of the same helix or between residues of the two chains of the double helix. 13C NMR parameter calculations have revealed the impact of such a network on the chemical shifts of carbon atoms. In addition, DFT calculations using periodic boundary conditions were compulsory to highlight the presence of two types of sugar within the crystal sample. It allows us to confirm, theoretically, the experimental hypothesis that the existence of two distinct sugar types in the NMR spectrum is a consequence of crystal packing.
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