A DFT study on the mono lithium and sodium salts of N-(2-hydroxyphenyl)salicylaldimine

This computational organic chemistry study presents results based on density functional theory at the B3LYP/6-31G(d) and B3LYP/cc-PVTZ//B3LYP/6-31G(d) levels of theory. Other computational procedures (HF and MP2) are presented for model structures. Three main points were investigated: some of the electronic structure aspects, the relative stability of isomers, and aromaticity. The results suggest that the title salts are the first Schiff base systems in the literature to exist only in the N-H form, which is characterized as the zwitterion form. Also, the estimated delocalization of the π-electron density in the middle ring indicates that these compounds are the first examples of metalla-hetero[10]annulenes. Analysis of the electron density delocalization indicates that the title compounds are better conductors at the molecular level than the parent Schiff base, and therefore, can be considered as new building blocks for organic materials.     

Plant-Based Indole Alkaloids: A Comprehensive Overview from a Pharmacological Perspective

Plant-based indole alkaloids are very rich in pharmacological activities, and the indole nucleus is considered to contribute greatly to these activities. This review’s fundamental objective is to summarize the pharmacological potential of indole alkaloids that have been derived from plants and provide a detailed evaluation of their established pharmacological activities, which may contribute to identifying new lead compounds. The study was performed by searching various scientific databases, including Springer, Elsevier, ACS Publications, Taylor and Francis, Thieme, Wiley Online Library, ProQuest, MDPI, and online scientific books. A total of 100 indole compounds were identified and reviewed. The most active compounds possessed a variety of pharmacological activities, including anticancer, antibacterial, antiviral, antimalarial, antifungal, anti-inflammatory, antidepressant, analgesic, hypotensive, anticholinesterase, antiplatelet, antidiarrheal, spasmolytic, antileishmanial, lipid-lowering, antimycobacterial, and antidiabetic activities. Although some compounds have potent activity, some only have mild-to-moderate activity. The pharmacokinetic profiles of some of the identified compounds, such as brucine, mitragynine, 7-hydroxymitragynine, vindoline, and harmane, were also reviewed. Most of these compounds showed promising pharmacological activity. An in-depth pharmacological evaluation of these compounds should be performed to determine whether any of these indoles may serve as new leads.     

Longitudinal magnetic resonance imaging of spinal cord injury in mouse: changes in signal patterns associated with the inflammatory response

Contusion-type spinal cord injury (SCI) in mice was followed longitudinally using in vivo magnetic resonance (MR) imaging along with neurobehavioral tests performed on postinjury Days 1, 7, 14 and 28. Magnetic resonance images were acquired from seven injured wild-type mice using a 9.4-T scanner and presented in sagittal and axial views to reflect the current state of the injured cord neuropathology on each day. The data were analyzed individually to gain more insights on the neuroinflammatory response unique to the mouse, to characterize the spatiotemporal evolution of the lesion and to quantify the changes in lesion volume and length with time. The MR intensity patterns on Day 1 showed acute injuries as focal in one group of three mice and as diffuse in the remaining group of four mice. The focal injuries appeared as a region of hypointensity with well-defined boundaries. These injuries first enlarged on Day 7, but then shrunk slightly by Days 14 and 28. In contrast, the diffuse injuries were initially obscure on Day 1, mainly because of loss of contrast between gray and white matters. On Day 7, lesions expanded asymptotically in both rostral and caudal directions with respect to the epicenter, and maintained its size on Days 14 and 28. Previous studies based on postmortem histological analysis have reported lesions behaving more like in the focal group. However, this new injury with diffuse characteristics may have important implications for SCI research carried out with mice. Unique experiments on genetically engineered mice with altered neuroinflammatory response should help clarify the origin of these differences in the lesion formation.     

The effect of respiratory oscillations in heart rate on detrended fluctuation analysis

Characterization of heart rate using detrended fluctuation analysis (DFA) is impeded by respiratory oscillations. In particular, the short-term exponent measured from 15 to 30 beats is compromised in the DFA. We reconstruct respiratory signal from electrocardiograms and attenuate the respiratory oscillation in the heart rate using a frequency-dependent subtraction approach. We validate this method by applying it to an electrocardiogram signal simulated using a coupled differential equation with the respiratory oscillation modelled using a sine function. The exponent estimated using the proposed approach agreed with the exponent incorporated in the model within a narrow range. In contrast, the exponent obtained from the raw data deviated from the expected value. Furthermore, the exponents obtained for the raw heart rate are smaller than the exponents obtained for the respiration oscillation attenuated heart rate. We apply this approach to heart rate measured from 12 preterm infants that were being treated for prematurity related complications. As observed in the simulated data, we show that compared to the raw heart rate, the respiratory oscillation attenuated heart rate shows higher short-term exponent (p < 0.001).     

Estimating Drift Parameters in a Sub-Fractional Vasicek-Type Process

This study deals with drift parameters estimation problems in the sub-fractional Vasicek process given by dxt=θ(μ−xt)dt+dStH, with θ>0, μ∈R being unknown and t≥0; here, SH represents a sub-fractional Brownian motion (sfBm). We introduce new estimators θ^ for θ and μ^ for μ based on discrete time observations and use techniques from Nordin–Peccati analysis. For the proposed estimators θ^ and μ^, strong consistency and the asymptotic normality were established by employing the properties of SH. Moreover, we provide numerical simulations for sfBm and related Vasicek-type process with different values of the Hurst index H.     

What can the geometry tell about the charge distribution in the mesoionic heterocycles? A DFT study on the SCN4R2 system

This computational organic chemistry study was performed using the hybrid functional B3LYP. Many basis sets were evaluated and the basis set 6‐31G(d) was found to be the most practical in terms of time and accuracy. The study presents the first method in the chemical literature that allows estimation of submolecular charges in mesoionic compounds. The theory was built on a reference model structure for which the absolute value of charge of the aromatic p‐orbitals is known. This is the cornerstone, and by employing the harmonic oscillator model of aromaticity (HOMA) many parameters can be quantified. The electronic structure of the title compound was the subject of this approach. The study addressed the following points: geometries, infrared frequencies, NMR chemical shifts, calculated charges, a chemical reactivity, and the frontier orbitals. The calculations illustrate that the π‐system of the CN₄ segment includes considerable aromatic character and carries a positive charge while the overall charge is negative. This allows classifying it as a σ‐acceptor/π‐donor while the exocyclic counter anion, the sulfur atom, is a σ‐donor/π‐acceptor. The substituents (R groups) in this case are only σ‐donors. The approach may be applied to other mesoionic and mesoaromatic systems. Copyright © 2009 John Wiley & Sons, Ltd.     

Ieodoglucomides A and B from a marine-derived bacterium Bacillus licheniformis

Ieodoglucomides A (1) and B (2), unique glycolipopeptides consisting of an amino acid, a new fatty acid, a succinic acid, and a sugar, were isolated from a Marine-derived bacterium Bacillus licheniformis. The absolute stereochemistry of 1 and 2 was determined by deploying coupling constants, Marfey's and Mosher's methods, and literature reviews. Compounds 1 and 2 displayed moderate in vitro antimicrobial activity. Furthermore, ieodoglucomide B (2) exhibited cytotoxic activity against lung cancer and stomach cancer cell lines with GI(50) values of 25.18 and 17.78 μg/mL, respectively.     

Specific interactions and binding free energies between thermolysin and dipeptides: molecular simulations combined with ab initio molecular orbital and classical vibrational analysis

Thermolysin (TLN) is a metalloprotease widely used as a nonspecific protease for sequencing peptide and synthesizing many useful chemical compounds by the chemical industry. It was experimentally shown that the activity and functions of TLN are inhibited by the binding of many types of amino acid dipeptides. However, the binding mechanisms between TLN and dipeptides have not been clarified at the atomic and electronic levels. In this study, we investigated the binding mechanisms between TLN and four dipeptides. Specific interactions and binding free energies (BFEs) between TLN and the dipeptides were calculated using molecular simulations based on classical molecular dynamics and ab initio fragment molecular orbital (FMO) methods. The molecular systems were embedded in solvating water molecules during calculations. The calculated BFEs were qualitatively consistent with the trend of the experimentally observed inhibition of TLN activity by binding of the dipeptides. In addition, the specific interactions between the dipeptides and each amino acid residue of TLN or solvating water molecules were elucidated by the FMO calculations.     

The effects of L-shaped heat source in a quarter-tube enclosure filled with MHD nanofluid on heat transfer and irreversibilities,using LBM: numerical data,optimization using neural network algorithm (ANN)

Journal of Thermal Analysis and Calorimetry - In this paper, the process of natural convection heat transfer (NCHT) and production of entropy (POF) in a portion of a tube has been modeled...     

Study of capabilities of the ANN and RSM models to predict the thermal conductivity of nanofluids containing SiO2 nanoparticles

Journal of Thermal Analysis and Calorimetry - In this paper, thermal conductivity prediction of nanofluids is discussed by the RSM and ANN models. The nanofluids contain SiO2 nanoparticles, and...