DFT calculations, structural analysis, solvent effects, and non-covalent interaction study on the para-aminosalicylic acid complex as a tuberculosis drug: AIM, NBO, and NMR analyses.

In this study, the effect of non-covalent interactions on the para-aminosalicylic acid complex is explored using density functional theory (DFT) in the gas phase and the solution. Our findings exhibit that the achieved binding energies considerably change on going from the gas phase to the solution. Based on the obtained results, the absolute value of the binding energy of the complex in the polar solvents is lower than the non-polar ones while in the gas phase it is higher than the solution. The atoms in molecules (AIM) and the natural bond orbital (NBO) analyses are applied to estimate the topological properties and the charge transfer during complexation, respectively. The results indicate that the presence of the cation-π interaction increases the strength of the intramolecular hydrogen bond in the studied complex. Finally, the various electronic descriptors such as energy gap, hardness, softness, and electronic chemical potential are investigated to gain further insight into these interactions. According to the achieved results, the high energy gap of the complex in the water solvent indicates high chemical stability and low reactivity compared to the others. On the other hand, the most reactive as well as the softest complex belongs to the gas phase.

Methods for Direct Reductive N-Methylation of Nitro Compounds.

Direct reductive N-methylation of inexpensive and readily available nitro compounds as raw material feedstocks is more attractive and straightforward compared with conventional N-methylation of amines to prepare biologically and pharmaceutically important N-methylated amine derivatives. This strategy for synthesis of N-methylamines avoids prepreparation of NH-free amines and therefore significantly shortens the separation and purification steps. In recent years, numerous methylating agents and catalytic systems have been reported for this appealing transformation. Thus, it is an appropriate time to summarize such advances. This review elaborates on the most important discoveries and advances in this research arena, with special emphasis on the mechanistic aspect of reactions that may provide new insights into catalyst improvement.

Density functional theory studies on C20 with substitutional TinNn impurities.

In this paper, we have performed systematic theoretical surveys of C20 and its C20-2nTinNn nanocages with n = 1-8 at DFT. Full optimization indicates none of the structures collapse to open deformed as segregated heterofullerene. Also, in order to avoid the resulted strain of fused five-pentagon configuration, some of them deform their cage at the Ti-N bonds and appear cubic-like. Binding energy (Eb) increases, and the absolute heat of atomization │ΔHat│ of the designed C20-2nTinNn structures decreases, respectively, as the number of substituting Ti-N units increases. The calculated Eb of 57.05 eV/atom and │ΔHat│ of 2437.40 kcal/mol display C4Ti8N8 as the most thermodynamic stable heterofullerene where including eight separated Ti-N units through two double C═C bonds. In contrast, the calculated band gap of 2.06 eV shows C18Ti1N1 as the best-insulated heterofullerene. Here isolable or extractable open-shell C18Ti1N1 heterofullerene must be kinetic stable species, and closed-shell C4Ti8N8 should be thermodynamic stable species. Compared to the suggested Ti-decorated B38 fullerene as a high capacity hydrogen storage material with large Eb (5.67 eV/atom), our studied C20-2nTinNn heterofullerenes show the higher Eb with a range of 13.78 to 57.05 eV/atom, the higher stability, and the higher capacity hydrogen storage. Each Ti-N unit can bind up to two hydrogen molecules with an average adsorption energy of 0.073 eV/H2. While the C4Ti8N8 fullerene substituted with 8 Ti-N units can store 16 H2 molecules, the hydrogen gravimetric density (the hydrogen storage capacity) reaches up to 5.61 wt% with an average adsorption energy of 0.587 eV/H2. Based on these results, we infer that C4Ti8N8 fullerene is a potential material for hydrogen storage with high capacity and might motivate active experimental efforts in designing hydrogen storage media.

Selective adsorption and dissociation of NO, NO2, and N2O molecules on Si-doped haeckelite boron nitride nanotube: an investigation for sensitive molecular sensors and catalysts.

The current study describes the investigation of the adsorption NO, N2O, and NO2 on haeckelite boron nitride nanotube doped with Si (Si-doped haeck-BNNT) by means of density functional theory calculation (DFT). The obtained results confirmed the energetic stability of the optimized geometries and revealed that the adsorption of the gas molecules with the nanotube sidewall is a spontaneous process. The calculated work function of Si-doped haeck-BNNT in the presence of gas molecules is greater than that of a bare Si-doped haeck-BNNT sheet. The energy gap of the Si-doped haeck-BNNT is sensitive to the adsorption of the gas molecules, which implies possible future applications in gas sensors. For most of the adsorption configurations studied, the adsorption energies for the SiB-doped haeck-BNNT are higher than those for SiN-doped haeck-BNNTones. The N2O gas molecule is totally dissociated into N2 and O species through the adsorption process, while the other gas molecules retain their molecular forms. Thus, the SiN-doped haeck-BNNT is a likely catalyst for dissociation of the N2O gas molecule. Our findings divulge promising potential of the doped haeck-BNNT as a highly sensitive molecular sensor for NO and NO2 detection and a catalyst for N2O dissociation.

Quantum chemical studies of mercaptan gas detection with calcium oxide nanocluster.

The electronic sensitivity and adsorption behavior for mercaptan natural gas of a Ca12O12 nanocluster were studied via ab initio computations. To be more specific, to fully grasp the influence of mercaptan molecules on the chemical and electronic features of Ca12O12 nanocluster, some parameters, namely, charge transfer of natural bond orbital, molecular electrostatic potential, binding energies, and frontier molecular orbitals, are computed. The interaction between CH4S molecule and calcium atoms of Ca12O12 nanocluster through the sulfur head is strong. This strong interaction leads to a considerable transfer of charge from CH4S to the nanocluster. After mercaptan adsorption, the existing energy gap between two levels, the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of the nanostructure, dropped by 2.21 eV, illustrating that the dissociation process has extensively increased the electrical conductance of nanostructure. This electrical signal can help to detect CH4S molecules. Moreover, it could be concluded that Ca12O12 nanocluster has a short recovery time. In addition, solvent considerably influences the geometry factors and electronic features of CH4S/Ca12O12 complexes, and the interactions between species are significantly weaker in the aqueous medium compared with those in the vacuum.

Substitution effects via aromaticity, polarizability, APT, AIM, IR analysis, and hydrogen adsorption in C20-nTin nanostructures: a DFT survey.

In this paper, the substitution effects of titanium heteroatom(s) on aromaticity, the average isotropic polarizability (< α >), the atomic polar tensor (APT) charge, the electrostatic potential (ESP) map, and the atoms in molecule (AIM) analysis along with infrared (IR) spectroscopy of C20 fullerene and its C20-nTin derivatives (n = 1-5) are probed via density functional theory (DFT). The nucleus-independent chemical shifts (NICS) specify that substitution effect causes more aromaticity character of the optimized heterofullerenes than benzene molecule and higher APT charge distribution upon surfaces of them than pure cage. The highest negative and positive APT charge distribution on carbons of C15Ti5 and titanium substitutions of C16Ti4-2 implies that these sites can be attacked more readily by electrophilic and nucleophilic regents, respectively. We are very pleased to state that isolating the Ti-Ti single bonds by intermediacy of one or two C atoms is an applicable strategy for attaining the highest APT charge distribution on Ti atoms of C16Ti4-2 as suitable hydrogen storage. AIM analysis of the studied C20-nAln derivatives signifies the highest electron density (ρ (r)) of 0.294 a.u. and the highest positive Laplacian of electron density (∇2ρ (r)) of 0.190 a.u., at bond critical points (BCPs) of C-Ti bond in the most stable C19Ti1 species. This heterofullerene shows the lowest < α > between the studied structures. IR spectroscopy shows that exclusive of C16Ti4-1 (as transition state), the other optimized hollow cages (as global minima) have no imaginary frequency.

Investigation of fused remote N-heterocyclic silylenes (frNHSis), at DFT.

We compared and contrasted the ΔΕs-t, band gap (ΔΕHOMO-LUMO), aromaticity, charge distribution, and reactivity of singlet (s) and triplet (t) benzopyridine-4-ylidene as the fused remote N-heterocyclic carbene (frNHC) and frNHSis with different fused aromatic rings, at (U)B3LYP/AUG-cc-pVTZ and (U)M06-2X/AUG-cc-pVTZ levels of theory. In this investigation, we found (1) all s and t divalent states appear as minimum structures, for having no negative force constant. Nonetheless, only singlets present more thermodynamic stability than their triplet analogous; (2) the trend of ΔΕs-t in kcal/mol is ortho-pyrrole (52.94) > ortho-furan (51.84) > ortho-thiophene (50.38) > para-furan (49.36) > para-pyrrole (49.00) > para-phosphole (48.67) ≥ para-thiophene (48.64) > benzene (44.33) > ortho-phosphole frNHSi (27.50), while ΔΕs-t of frNHC is 15.65 kcal/mol; (3) apart from phosphole frNHSis, the order of ΔΕs-t in a "ortho position or zigzag array" about 1.8-4.0 kcal/mol is more than that of in a "para position or chair array"; (4) the highest ΔΕHOMO-LUMO is demonstrated by ortho-pyrrole frNHSi (95.65 kcal/mol) while the lowest ΔΕHOMO-LUMO is verified by the reference frNHC (63.44 kcal/mol); (5) in contradiction of frNHC, all singlet frNHSis reveal higher band gap and lower global reactivity than their triplet congeners; (6) charge distribution along with MEP maps indicate differentially electronic cloud in middle of rings frNHSis vs. frNHC; (7) we anticipate higher nucleophilicity and lower electrophilicity of triplet frNHSis than singlet congeners, will make them worthy of synthetic surveys.

Characterization of titanium influences on structure and thermodynamic stability of novel C20-nTin nanofullerenes (n=1-5): a density functional perspective.

In this survey, effects of titanium heteroatom(s) on structural parameters and thermodynamic stability of C20 fullerene and its C20-nTin derivatives (n = 1-5) are compared and contrasted, at DFT levels of theory. The results show that in going from C19Ti1 to C15Ti5, binding energy increases while absolute value heat of atomization decreases. According to vibrational frequency analysis, excepting C16Ti4-1, the other optimized structures give no imaginary frequency as true minima. The calculated binding energy of 887.12 kcal mol-1/atom displays C15Ti5 as the most thermodynamically stable heterofullerene. It has Cs symmetry and contains five titanium atoms alternatively in equatorial position. The substitutional doping of C20 fullerene leads to high Mülliken charge distribution upon the surfaces of the resulted heterofullerenes especially C19Ti1 as suitable hydrogen storage. The contour plots indicate the most negative electrostatic potential by red color for C atoms, whereas the most positive electrostatic potential by yellow color for Ti heteroatoms. The contour plots and multiwfn analysis exhibit charge transfer from titanium heteroatoms to the neighboring carbon atoms. Furthermore, the resulted electron density maps from multiwfn qualitatively confirm the contour plot's findings. The hydrogen adsorption is an endothermic process for C20 fullerene and exothermic process for C20-nTin heterofullerenes. Major criteria examined for thermodynamic stability; from C19Ti1 to C15Ti5, binding energy and hydrogen adsorption increase while heat of atomization decreases.

Direct synthesis of sulfenamides, sulfinamides, and sulfonamides from thiols and amines.

Needless to say that organosulfur compounds with sulfur-nitrogen bonds have found various applications in diverse fields such as pharmaceuticals, agrochemicals, polymers, and so forth. Three major groups of such compounds are sulfenamides, sulfinamides, and sulfonamides which have been widely applied as building blocks in medical chemistry. Owing to their significant role in drug design and discovery programs, the search for and development of efficient, environmentally friendly, and economic processes for the preparation of the title compounds is of great importance in the pharmaceutical industry. Recently, oxidative coupling of thiols and amines, two readily available low-cost commodity chemicals, has emerged as a highly useful method for synthesizing structurally diverse sulfenamides, sulfinamides, and sulfonamides in a single step. Since this strategy does not require additional pre-functionalization and de-functionalization steps, it considerably streamlines synthetic routes and substantially reduces waste generation. This review will focus on recent advances and achievements in this attractive research arena.

Alkoxysulfenylation of alkenes: development and recent advances.

Among the wide variety of synthetic transformations of inexpensive and abundant feedstock alkenes, vicinal difunctionalization of carbon-carbon double bonds represent one of the most powerful and effective strategies for the introduction of two distinct functional groups into target compounds in a one-pot process. In this context, the direct alkoxysulfenylation of alkenes has emerged as an elegant method to construct valuable ß-alkoxy sulfides in an atom- and pot-economic manner utilizing readily accessible starting materials. Here, we review the available literature on this appealing research topic by hoping that it will be beneficial for eliciting further research and thinking in this domain.

The recent development of donepezil structure-based hybrids as potential multifunctional anti-Alzheimer's agents: highlights from 2010 to 2020.

Dementia is a term used to define different brain disorders that affect memory, thinking, behavior, and emotion. Alzheimer's disease (AD) is the second cause of dementia that is generated by the death of cholinergic neurons (especially acetylcholine (ACh)), which have a vital role in cognition. Acetylcholinesterase inhibitors (AChEI) affect acetylcholine levels in the brain and are broadly used to treat Alzheimer's. Donepezil, rivastigmine, and galantamine, which are FDA-approved drugs for AD, are cholinesterase inhibitors. In addition, scientists are attempting to develop hybrid molecules and multi-target-directed ligands (MTDLs) that can simultaneously modulate multiple biological targets. This review highlights recent examples of MTDLs and fragment-based strategy in the rational design of new potential AD medications from 2010 onwards.

Progress and recent trends in the direct selenocyanation of (hetero)aromatic C-H bonds.

This review covers recent advances in the direct selenocyanation of (hetero)aromatic C-H bonds with an emphasis on the reaction mechanisms. This novel approach is an effective means of preparing a variety of aromatic and heteroaromatic selenocyanates, which are extremely versatile synthetic precursors of selenium-containing compounds, such as selenols, seleninic acids, selenides, diselenides, and trifluoromethyl selenides.

Recent trends in dehydroxylative trifluoro-methylation, -methoxylation, -methylthiolation, and -methylselenylation of alcohols.

Owing to the prevalence of hydroxyl groups on molecules, much attention has been paid to the synthesis of functionalized organic compounds by dehydroxylative functionalization of parent alcohols. In this context, dehydroxylative trifluoromethylation, trifluoromethoxylation, trifluoromethylthiolation, and trifluoromethylselenylation of readily available alcohols have recently emerged as intriguing protocols for the single-step construction of diverse structures bearing C-CF3, C-OCF3, C-SCF3, and C-SeCF3 bonds, respectively. This Mini-Review aims to summarize the major progress and advances in this appealing research area with special emphasis on the mechanistic features of the reaction pathways.

Hydroxysulfonylation of alkenes: an update.

The direct difunctionalization of inexpensive and widely available alkenes has been recognized as a strong and straightforward tool for the rapid fabrication of complex molecules and pharmaceutical targets by introducing two different functional groups on adjacent carbon atoms of common alkene moieties in a single operation. This synthetic strategy avoids the purification and isolation of the intermediates and thus makes synthetic schemes shorter, simpler and cleaner. In this family of reactions, the hydroxysulfonylation of alkenes has emerged as an increasingly promising strategy for the synthesis of ß-hydroxysulfones, which are found in many biologically important molecules and widespread applications in organic synthesis. The objective of this review is to illustrate the advancements in the field of hydroxysulfonylation of alkenes with special emphasis on the mechanistic details of the reaction pathways.

Knockdown of Angiopoietin-like protein 4 suppresses the development of colorectal cancer.

Colorectal cancer, is the growth of cancer cells in the part of the colon. Angiopeptin is one of the growth factors in the human body that is particularly effective in the regulatory process. In this research, the regulatory role and its mechanism of Angiopoietin-like protein 4 (ANGPTL4) in colorectal cancer (CRC) metastasis, has been studied. Protein expression of ANGPLT4 was analyzed by immunohistochemistry in tumor samples and adjacent normal specimens of 40 patients with CRC cancer of various phases. A gene knockout test was conducted, two effective siRNA of ANGPTL4, named siRNA1 and siRNA2, were constructed and transfected into two CRC cell lines SW480 and HT-29 to block the expression of ANGPTL4. QRT-PCR and western blotting were used to validate the knockdown efficiency of the mRNA and proteins. Based on the results, the protein expression of ANGPTL4 was increased in human CRC tissues with the development of CRC. Knockdown of ANGPTL4 by siRNA in SW480 and HT-29 cells in vitro inhibited cell proliferation, promoted cell apoptosis, and suppressed the ability of cell migration and invasion. Besides, the sensitivity of CRC cells to Cisplatin was increased in the low ANGPTL4 expression group. ANGPTL4 might be a new potential therapeutic target for patients with CRC.

The application of DNA molecular markers in the study of Codonopsis species genetic variation, a review.

Codonopsis genus is comprised of species that are perennial plants primarily distributed across all east, southeast, and Central Asia. The most famous species of Codonopsis are C. tangshen, C. lanceolate, and C. pilosula. The records showed that they have a long story usage as traditional Chinese medicines, as they were alleged to be able to intensify the spleen and the lung as well as enriching blood and engendering liquid. Certain species have a culinary value in southern China and Southeast Asia, where they are considered as tea, wine, soup, plaster, and porridge. Codonopsis species were shown to be of great importance in medicine, due to their broad biological activity. Therefore, a clear understanding of their genetic diversity is needed.  Adequate distinctions and descriptions of those species are necessary to preserve plant reservoir, investigations of genes associated with desirable traits, and understanding of evolutionary relationships. Subsequently, various molecular marker techniques such as Random Amplified Polymorphic DNA (RAPD), Amplified Fragment Length Polymorphism (AFLP), Simple Sequence Repeats (SSR), and Inter Simple Sequence Repeat (ISSR), Single Nucleotide Polymorphism (SNP), internal transcribed spacer (ITS), and Sequence-Characterized Amplified Region (SCAR) have been improved to provide  detailed informations about genomes, that historically were  not possible to obtain based on only phenotypic methods. This review represents the usage of DNA molecular markers for molecular diversity analysis of medically important species belonging to the genus Codonopsis.

One-pot synthesis of 2-amino-4H-chromene derivatives by MNPs@Cu as an effective and reusable magnetic nanocatalyst.

In this research, MNPs@Cu as an effective and recyclable nanocatalyst was prepared and characterized using different methods including Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), vibrating sample magnetometry (VSM), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), and X-ray diffraction (XRD). After the characterization of this new nanocatalyst, it was efficiently used for the promotion of the one-pot synthesis of 2-amino-4H-chromene derivatives via one-pot three-component reaction of the enolizable compound, malononitrile, and arylaldehydes under solvent-free conditions at 90 °C. The procedure gave the desired products in high-to-excellent yields in short reaction times. Also this catalyst, because of its magnetic nature, can be simply restored by a permanent magnetic field and comfortably reused several times without any significant loss of its catalytic activity.

Methods for direct C(sp2)-H bonds azidation.

Direct functionalization of C-H bonds has attracted great attention in recent years from the perspectives of atom and step economy. In this context, a variety of processes have been developed for the construction of synthetically and biologically important organic azides through the oxidative C-H bonds azidation. In this review, we have summarized recent progress in the direct azidation of C(sp2)-H bonds. The review is divided into three major sections: (i) direct azidation of aromatic C-H bonds; (ii) direct azidation of olefinic C-H bonds; and (iii) direct azidation of aldehydic C-H bonds. Mechanistic aspects of the reactions are considered and discussed in detail.

Hydrogen and syngas production by catalytic gasification of algal biomass (Cladophora glomerata L.) using alkali and alkaline-earth metals compounds.

The steam gasification of algal biomass (Cladophora glomerata L.) in presence of alkali and alkaline-earth metal compounds catalysts was studied to enhance the yield of syngas and reduce its tar content through cracking and reforming of condensable fractions. The commercial catalysts used include NaOH, KHCO3, Na3PO4 and MgO. The gasification runs carried out with a research scale, biomass gasification unit, show that the NaOH has a strong potential for production of hydrogen, along with the added advantages of char converting and tar destruction, allowing enhancement of produced syngas caloric value. When the temperature increased from 700°C to 900°C, the tar content in the gas sharply decreased, while the hydrogen yield increased. Increasing steam/biomass ratio significantly increased hydrogen yield and tar destruction; however, the particle size in the range of 0.5-2.5 mm played a minor role in the process.

Gasification of algal biomass (Cladophora glomerata L.) with CO2/H2O/O2 in a circulating fluidized bed.

Gasification is one of the most important thermochemical routes to produce both synthesis gas (syngas) and chars. The quality of produced syngas wieldy depends on the operating conditions (temperature, residence time, heating rate, and gasifying agent), hydrodynamic properties of gasifier (particle size, minimum fluidization velocity, and gasifier size), and type of feedstock (coal, biomass, oil, and municipal solid wastes). In the present study, simulation of syngas production via circulating fluidized bed (CFB) gasification of algal biomass (Cladophora glomerata L.) at different gasifying agents and particle sizes was carried out, using Aspen Plus simulator. The model which has been validated by using experimental data of the technical literature was used to evaluate the influence of operating conditions on gas composition and performance parameters. The results show that biomass gasification using pure oxygen as the gasification agent has great potential to improve the caloric value of produced gas and performance indicators. It was also found that the produced gas caloric value, syngas yield, and performance parameters (CCE and CGE) increase with reaction temperature but are inversely proportional to the biomass particle size.