NMR study of the stoichiometry and stability of complexation reaction between Mg2+, Ca2+, Sr2+ and Ba2+ ions and 60-crown-20 in binary acetonitrile solvent mixtures

Proton nuclear magnetic resonance (¹H-NMR) spectroscopy was used to study the complexation reaction between Mg²⁺, Ca²⁺, Sr²⁺ and Ba²⁺ ions and 60-crown-20 in a series of binary mixtures of deuterated acetonitrile (AN), nitromethane (NM) and D₂O at 27?°C. Formation constants of the 1:1 complexes were determined through computer fitting of the chemical shift/mol ratio data and found to vary in the order of Ba²⁺?>?Sr²⁺?>?Mg²⁺?≈?Ca²⁺. The influence of the solvent composition on the stability of the resulting complexes was also discussed. In all cases, the changes in the stability constants with the solvent composition were monotonic and showed a good correlation with the inherent solvation ability of the pure solvents which form the mixture.     

Edge-shared [M2Cl10]2? complexes of reaction between oxophilic group 4 metal and phosphorus ylides

The reactions between oxophilic group 4 metal chlorides, ??-keto ylides in THF, led to the formation of titanium, zirconium and hafnium edge-shared [M₂Cl₁₀]^2? complexes (1a?C3f). We describe that the reaction between MCl₄ (M = Ti, Zr and Hf) with phosphorus ylides produce edge-shared [M₂X₁₀]^2? complexes instead of O-coordination previously reported complexes. Adding dimethyl sulfoxide (DMSO) to these complexes in room temperature crystalline solid [M(DMSO)₈] · 4Cl · mH₂O · DMSO] (M = Ti (1g), Zr (2g) and Hf (3g); m = 0?C3) together with phosphonium salts in mother liquid were formed. The compounds were characterized by elemental analysis, IR and ¹H, ¹³C and ³¹P NMR spectroscopy.     

Polymer translocation in solid-state nanopores: dependence of scaling behavior on pore dimensions and applied voltage

We investigate unforced and forced translocation of a Rouse polymer (in the absence of hydrodynamic interactions) through a silicon nitride nanopore by three-dimensional Langevin dynamics simulations, as a function of pore dimensions and applied voltage. Our nanopore model consists of an atomistically detailed nanopore constructed using the crystal structure of β-Si(3)N(4). We also use realistic parameters in our simulation models rather than traditional dimensionless quantities. When the polymer length is much larger than the pore length, we find the translocation time versus chain length scales as τ ～ N(2+ν) for the unforced case and as τ ～ N((1+2ν)/(1+ν)) for the forced case. Our results agree with theoretical predictions which indicate that memory effects and tension on the polymer chain play an important role during the translocation process. We also find that the scaling exponents are highly dependent on the applied voltage (force). When the length of the polymer is on the order of the length of the pore, we do not find a continuous scaling law, but rather scaling exponents that increase as the length of the polymer increases. Finally, we investigate the scaling behavior of translocation time versus applied voltage for different polymer and pore lengths. For long pores, we obtain the theoretical scaling law of τ ～ 1/V(α), where α ? 1 for all voltages and polymer lengths. For short pores, we find that α decreases for very large voltages and/or small polymer lengths, indicating that the value of α = 1 is not universal. The results of our simulations are discussed in the context of experimental measurements made under different conditions and with differing pore geometries.     

Molecular structure and character of bonding of mono and divalent metal cations (Li+, Na+, K+, Mg2+, Ca2+, Zn2+, and Cu+) with guanosine: AIM and NBO analysis

The B3LYP/6-311++G (d,p) density functional approach was used to study the gas-phase metal affinities of Guanosine (ribonucleoside) for the Li⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺, Zn²⁺, and Cu⁺ cations. In this study we determine coordination geometries, binding strength, absolute metal ion affinities, and free energies for the most stable products. We have also compared the results for Guanosine, with our previously reported results for 2′-Deoxyguanosine. Based on the results, it is obvious that MIA is strongly dependent on the charge-to-size ratio of the cation. Guanosine interacts more strongly with Zn²⁺ than do with Mg²⁺, Ca²⁺, and Cu⁺ and therefore stronger interactions lead to higher MIA. In both free molecules and their complexes, the Syn orientation of the base is stabilized by an intramolecular O5′–H···N3 hydrogen bond and the anti orientation of the base is stabilized by an intramolecular C–H···O hydrogen bond formed between the (C8-H8) and the O5′ atom of the sugar moiety. It is also interesting to mention that linear correlation between calculated MIA values and the atomic numbers (Z) of the metal ions of Li⁺, Na⁺, and K⁺ were found. Furthermore, the influences of metal cationization on the strength of the N-glycosidic bond, torsion angles, angle of pseudorotation (P), and intramolecular C–H···O and O–H···O hydrogen bonds have been studied. Natural bond orbital (NBO) analysis was performed to calculate the charge transfer and natural population analysis of the complexes. Quantum theory of atoms in molecules (QTAIM) was also applied to determine the nature of interactions.     

Structuring product development processes

This paper proposes operational frameworks for structuring product development processes. The primary objective of this research is to develop procedures to minimize iterations during the development process which adversely affect development time and costs. Several procedures are introduced to restructure the development process. The computation of the corresponding product development times is facilitated by two Markov models addressing different types of learning. The methodologies are employed to identify a set of managerial concerns in restructuring the product development processes.The developed framework has become an integral part of a re-engineering project for the development of rocket engines at Rocketdyne Division of Rockwell International. Throughout the paper, the methodologies are illustrated with the help of this process.     

Schemes for Single Electron Transistor Based on Double Quantum Dot Islands Utilizing a Graphene Nanoscroll,Carbon Nanotube and Fullerene

The single electron transistor (SET) is a nanoscale switching device with a simple equivalent circuit. It can work very fast as it is based on the tunneling of single electrons. Its nanostructure contains a quantum dot island whose material impacts on the device operation. Carbon allotropes such as fullerene (C₆₀), carbon nanotubes (CNTs) and graphene nanoscrolls (GNSs) can be utilized as the quantum dot island in SETs. In this study, multiple quantum dot islands such as GNS-CNT and GNS-C₆₀ are utilized in SET devices. The currents of two counterpart devices are modeled and analyzed. The impacts of important parameters such as temperature and applied gate voltage on the current of two SETs are investigated using proposed mathematical models. Moreover, the impacts of CNT length, fullerene diameter, GNS length, and GNS spiral length and number of turns on the SET’s current are explored. Additionally, the Coulomb blockade ranges (CB) of the two SETs are compared. The results reveal that the GNS-CNT SET has a lower Coulomb blockade range and a higher current than the GNS-C₆₀ SET. Their charge stability diagrams indicate that the GNS-CNT SET has smaller Coulomb diamond areas, zero-current regions, and zero-conductance regions than the GNS-C₆₀ SET.     

Antiviral Activities of Algal-Based Sulfated Polysaccharides

An antiviral agent is urgently needed based on the high probability of the emergence and re-emergence of future viral disease, highlighted by the recent global COVID-19 pandemic. The emergence may be seen in the discovery of the Alpha, Beta, Gamma, Delta, and recently discovered Omicron variants of SARS-CoV-2. The need for strategies besides testing and isolation, social distancing, and vaccine development is clear. One of the strategies includes searching for an antiviral agent that provides effective results without toxicity, which is well-presented by significant results for carrageenan nasal spray in providing efficacy against human coronavirus-infected patients. As the primary producer of sulfated polysaccharides, marine plants, including macro- and microalgae, offer versatility in culture, production, and post-isolation development in obtaining the needed antiviral agent. Therefore, this review will describe an attempt to highlight the search for practical and safe antiviral agents from algal-based sulfated polysaccharides and to unveil their features for future development.     

Energy,Exergy, Exergoeconomic and Emergy-Based Exergoeconomic (Emergoeconomic) Analyses of a Biomass Combustion Waste Heat Recovery Organic Rankine Cycle

In recent decades, there has been an increasing trend toward the technical development of efficient energy system assessment tools owing to the growing energy demand and subsequent greenhouse gas emissions. Accordingly, in this paper, a comprehensive emergy-based exergoeconomic (emergoeconomic) method has been developed to study the biomass combustion waste heat recovery organic Rankine cycle (BCWHR-ORC), taking into account thermodynamics, economics, and sustainability aspects. To this end, the system was formulated in Engineering Equation Solver (EES) software, and then the exergy, exergoeconomic, and emergoeconomic analyses were conducted accordingly. The exergy analysis results revealed that the evaporator unit with 55.05 kilowatts and the turbine with 89.57% had the highest exergy destruction rate and exergy efficiency, respectively. Based on the exergoeconomic analysis, the cost per exergy unit (c), and the cost rate (C˙) of the output power of the system were calculated to be 24.13 USD/GJ and 14.19 USD/h, respectively. Next, by applying the emergoeconomic approach, the monetary emergy content of the system components and the flows were calculated to evaluate the system’s sustainability. Accordingly, the turbine was found to have the highest monetary emergy rate of capital investment, equal to 5.43×1012 sej/h, and an output power monetary emergy of 4.77×104 sej/J. Finally, a sensitivity analysis was performed to investigate the system’s overall performance characteristics from an exergoeconomic perspective, regarding the changes in the transformation coefficients (specific monetary emergy).     

Synthesis of 2D Germanane (GeH): a New,Fast, and Facile Approach

Germanane (GeH), a germanium analogue of graphane, has recently attracted considerable interest because its remarkable combination of properties makes it an extremely suitable candidate to be used as 2D material for field effect devices, photovoltaics, and photocatalysis. Up to now, the synthesis of GeH has been conducted by substituting Ca by H in a β‐CaGe₂ layered Zintl phase through topochemical deintercalation in aqueous HCl. This reaction is generally slow and takes place over 6 to 14 days. The new and facile protocol presented here allows to synthesize GeH at room temperature in a significantly shorter time (a few minutes), which renders this method highly attractive for technological applications. The GeH produced with this method is highly pure and has a band gap (E_g) close to 1.4 eV, a lower value than that reported for germanane synthesized using HCl, which is promising for incorporation of GeH in solar cells.