Matrix Isolation FTIR and Theoretical Study of Weakly Bound Complexes of Isocyanic Acid with Nitrogen

Weak complexes of isocyanic acid (HNCO) with nitrogen were studied computationally employing MP2, B2PLYPD3 and B3LYPD3 methods and experimentally by FTIR matrix isolation technique. The results show that HNCO interacts specifically with N2. For the 1:1 stoichiometry, three stable minima were located on the potential energy surface. The most stable of them involves a weak, almost linear hydrogen bond from the NH group of the acid molecule to nitrogen molecule lone pair. Two other structures are bound by van der Waals interactions of N⋯N and C⋯N types. The 1:2 and 2:1 HNCO complexes with nitrogen were computationally tracked as well. Similar types of interactions as in the 1:1 complexes were found in the case of the higher stoichiometry complexes. Analysis of the HNCO/N2/Ar spectra after deposition indicates that the 1:1 hydrogen-bonded complex is prevalent in argon matrices with a small amount of the van der Waals structures also present. Upon annealing, complexes of the 1:2 and 2:1 stoichiometry were detected as well.

One-pot synthesis of high-capacity silicon anodes via on-copper growth of a semi-conducting, porous polymer

Silicon-based anodes with lithium ions as charge carriers have the highest predicted theoretical specific capacity of 3579 mA h g (for LiSi). Contemporary electrodes do not achieve this theoretical value largely because conventional production paradigms rely on the mixing of weakly coordinated components. In this paper, a semi-conductive triazine-based graphdiyne polymer network is grown around silicon nanoparticles directly on the current collector, a copper sheet. The porous, semi-conducting organic framework (i) adheres to the current collector on which it grows via cooperative van der Waals interactions, (ii) acts effectively as conductor for electrical charges and binder of silicon nanoparticles via conjugated, covalent bonds, and (iii) enables selective transport of electrolyte and Li-ions through pores of defined size. The resulting anode shows extraordinarily high capacity at the theoretical limit of fully lithiated silicon. Finally, we combine our anodes in proof-of-concept battery assemblies using a conventional layered Ni-rich oxide cathode.

Long-Range Interactions for Hydrogen Atoms in Excited D States

Pressure shifts inside an atomic beam are among the more theoretically challenging effects in high-precision measurements of atomic transitions. A crucial element in their theoretical analysis is the understanding of long-range interatomic interactions inside the beam. For excited reference states, the presence of quasi-degenerate states leads to additional challenges, due to the necessity to diagonalize large matrices in the quasi-degenerate hyperfine manifolds. Here, we focus on the interactions of hydrogen atoms in reference states composed of an excited nD state (atom A), and in the metastable 2S state (atom B). We devote special attention to the cases n=3 and n=8. For n=3, the main effect is generated by quasi-degenerate virtual P states from both atoms A and B and leads to experimentally relevant second-order long-range (van-der-Waals) interactions proportional to the sixth inverse power of the interatomic distance. For n=8, in addition to virtual states with two states of P symmetry, one needs to take into account combined virtual P and F states from atoms A and B. The numerical value of the so-called C6 coefficients multiplying the interaction energy was found to grow with the principal quantum number of the reference D state; it was found to be of the order of 1011 in atomic units. The result allows for the calculation of the pressure shift inside atomic beams while driving transitions to nD states.

Palm Olein Organogelation Using Mixtures of Soy Lecithin and Glyceryl Monostearate

The present work investigated the interaction between soy lecithin (SL), glyceryl monostearate (GMS), and water in structuring palm olein (PO) to create an organogel having similar mechanical properties to commercial spread. Extreme vertices mixture design was used to optimize the composition of PO-based organogel. The resulting model showed a good fit to the predicted data with R2 ≥ 0.89. The optimum composition was 8% SL, 22% GMS, 28% water, and 42% PO (w/w) to produce a mean firmness of 1.91 N, spreadability of 15.28 N s−1, and oil binding capacity (OBC) of 83.83%. The OBC of optimized organogel was 10% higher than commercial spread product, and no significant difference was observed in the mechanical properties (p > 0.05). The microstructure, as well as the rheological and thermal properties of the optimized organogel were characterized. Fourier transform infrared analysis indicated that hydrogen bonding and van der Waals interactions were the key driving forces for organogelation. The mixture of SL and GMS favored the formation of β′ + β form crystals with a predominance of the β′ form. These results have important implications for the development of PO-based organogel as a potential fat replacer in the production of low-fat spread.

Crystal structure of N,N,N′,N′-tetramethylethanediamine

The title compound N,N,N′,N′-tetramethylethanediamine, C6H16N2, is a bidentate amine ligand commonly used in organolithium chemistry for deaggregation. Crystals were grown at 243 K from n-pentane solution. The complete molecule is generated by a crystallographic center of symmetry and the conformation of the diamine is antiperiplanar. To investigate the intermolecular interactions, a Hirshfeld surface analysis was performed. It showed that H...H (van der Waals) interactions dominate with a contact percentage of 92.3%.

A Review on Synthesis Methods of Phyllosilicate- and Graphene-Filled Composite Hydrogels

This review discusses, in brief, the various synthetic methods of two widely-used nanofillers; phyllosilicate and graphene. Both are 2D fillers introduced into hydrogel matrices to achieve mechanical robustness and water uptake behavior. Both the fillers are inserted by physical and chemical gelation methods where most of the chemical gelation, i.e., covalent approaches, results in better physical properties compared to their physical gels. Physical gels occur due to supramolecular assembly, van der Waals interactions, electrostatic interactions, hydrophobic associations, and H-bonding. For chemical gelation, in situ radical triggered gelation mostly occurs.

Carbon Nanotubes and its Application in Nanotechnology

Carbon nanotubes often refer to single-wall carbon nanotubes (SWCNTs) with diameters in the range of a nanometer. Single-wall carbon nanotubes are one of the allotropes of carbon, intermediate between fullerene cages and flat graphene. Carbon nanotubes also often refer to multi-wall carbon nanotubes(MWCNTs), consisting of nested single-wall carbon nanotubes, weakly bound together by van der Waals interactions in a tree ring-like structure. If not identical, these tubes are very similar to long straight and parallel carbon layers, cylindrically arranged around a hollow tube. Multi-wall carbon nanotubes are also sometimes used to refer to double and triple wall carbon nanotubes. Carbon nanotubes can also refer to tubes with an undetermined carbon wall structure and diameters less than 100 nanometers. While nanotubes of other compositions exist, most research has been focused on the carbon ones. The length of a carbon nanotube produced by common production methods is typically much larger than its diameter. Thus, for many purposes, end effects are neglected and the length of carbon nanotubes is assumed infinite. Carbon nanotubes can exhibit remarkable unique properties. These include electrical conductivity, while others are semiconductors. They also have exceptional tensile strengthand thermal conductivity, because of their nanostructure and strength of the bonds between carbon atoms. In addition, they can be chemically modified. Thus, due to their variable, unique properties, carbon nanotubes have found applications in many realms such as electronics, optics, composite materials nanotechnology, and other applications of materials science. In addition, carbon nanotubes can be integrated into other molecules to form novel structures with unique properties, different from the individual reactants. These unique products have also found application in many realms of nanotechnology

Phenanthroline Complexation Enhances the Cytotoxic Activity of the VO-Chrysin System

Metal complexation in general improves the biological properties of ligands. We have previously measured the anticancer effects of the oxidovanadium(IV) cation with chrysin complex, VO(chrys)2. In the present study, we synthesized and characterized a new complex generated by the replacement of one chrysin ligand by phenanthroline (phen), VO(chrys)phenCl, to confer high planarity for DNA chain intercalation and more lipophilicity, giving rise to a better cellular uptake. In effect, the uptake of vanadium has been increased in the complex with phen and the cytotoxic effect of this complex proved higher in the human lung cancer A549 cell line, being involved in its mechanisms of action, the production of cellular reactive oxygen species (ROS), the decrease of the natural antioxidant compound glutathione (GSH) and the ratio GSH/GSSG (GSSG, oxidized GSH), and mitochondrial membrane damage. Cytotoxic activity studies using the non-tumorigenic HEK293 cell line showed that [VO(chrys)phenCl] exhibits selectivity action towards A549 cells after 24 h incubation. The interaction with bovine serum albumin (BSA) by fluorometric determinations showed that the complex could be carried by the protein and that the binding of the complex to BSA occurs through H-bond and van der Waals interactions.

Effect of Dimensionality on The Electronic Properties of SnSe: A Density Functional Theory Study

This study investigated the structural and electronic properties of bulk, bilayer, and monolayer SnSe using the density functional theory (DFT) method. We succeeded in calculating the bandgap and identifying accurately the transformation of the band structure from bulk to monolayer systems using generalized gradient approximation. An increase in the lattice parameter a and a decrease in the lattice parameter b were observed when the bulk dimensions were reduced to a monolayer. The reduction of van der Waals interactions when the dimensions of a system are reduced is the main factor that causes changes in lattice parameters. The indirect bandgap of bulk SnSe (0.56 eV, 0.3∆→0.7Σ) becomes wider in the monolayer system (0.94 eV, 0.2∆→0.8Σ). Bandgap widening is predicted due to the emergence of the quantum confinement effect in low-dimensional systems. Furthermore, we found the formation of a quasi-degenerate minimum conduction band in the monolayer SnSe. With the formation of these bands, we predict the monolayer SnSe will have better thermoelectric properties than the bulk or bilayer system. This study provides an in-depth understanding of the electronic structure of SnSe and its correlation to thermoelectric properties.

Lipid Specific Membrane Interaction of Aptamers and Cytotoxicity

We aim to discover diagnostic tools to detect phosphatidylserine (PS) externalization on apoptotic cell surface using PS binding aptamers, AAAGAC and TAAAGA, and hence to understand chemotherapy drug efficacy when inducing apoptosis into cancer cells. The entropic fragment-based approach designed aptamers have been investigated to inspect three aspects: lipid specificity in aptamers’ membrane binding and bilayer physical properties-induced regulation of binding mechanisms, the apoptosis-induced cancer cell surface binding of aptamers, and the aptamer-induced cytotoxicity. The liposome binding assays show preferred membrane binding of aptamers due to presence of PS in predominantly phosphatidylcholine-contained liposomes. Two membrane stiffness reducing amphiphiles triton X-100 and capsaicin were found to enhance membrane’s aptamer adsorption suggesting that bilayer physical properties influence membrane’s adsorption of drugs. Microscopic images of fluorescence-tagged aptamer treated LoVo cells show strong fluorescence intensity only if apoptosis is induced. Aptamers find enhanced PS molecules to bind with on the surface of apoptotic over nonapoptotic cells. In cytotoxicity experiments, TAAAGA (over poor PS binding aptamer CAGAAAAAAAC) was found cytotoxic towards RBL cells due to perhaps binding with nonapoptotic externalized PS randomly and thus slowly breaching plasma membrane integrity. In these three experimental investigations, we found aptamers to act on membranes at comparable concentrations and specifically with PS binding manner. Earlier, we reported the origins of actions through molecular mechanism studies—aptamers interact with lipids using mainly charge-based interactions. Lipids and aptamers hold distinguishable charge properties, and hence, lipid–aptamer association follows distinguishable energetics due to electrostatic and van der Waals interactions. We discover that our PS binding aptamers, due to lipid-specific interactions, appear as diagnostic tools capable of detecting drug-induced apoptosis in cancer cells.