scholarly journals Neutrophil Immunomodulatory Activity of Natural Organosulfur Compounds

Molecules ◽  
2019 ◽  
Vol 24 (9) ◽  
pp. 1809 ◽  
Author(s):  
Igor A. Schepetkin ◽  
Liliya N. Kirpotina ◽  
Andrei I. Khlebnikov ◽  
Narayanaganesh Balasubramanian ◽  
Mark T. Quinn
Keyword(s):  
Density Functional ◽  
Glycogen Synthase ◽  
Frontier Molecular Orbital ◽  
Mustard Oil ◽  
Immunomodulatory Activity ◽  
Diallyl Disulfide ◽  
Organosulfur Compounds ◽  
Ros Production ◽  
Hl60 Cells ◽  
Dipropyl Disulfide

Organosulfur compounds are bioactive components of garlic essential oil (EO), mustard oil, Ferula EOs, asafoetida, and other plant and food extracts. Traditionally, garlic (Allium sativum) is used to boost the immune system; however, the mechanisms involved in the putative immunomodulatory effects of garlic are unknown. We investigated the effects of garlic EO and 22 organosulfur compounds on human neutrophil responses. Garlic EO, allyl propyl disulfide, dipropyl disulfide, diallyl disulfide, and allyl isothiocyanate (AITC) directly activated Ca2+ flux in neutrophils, with the most potent being AITC. Although 1,3-dithiane did not activate neutrophil Ca2+ flux, this minor constituent of garlic EO stimulated neutrophil reactive oxygen species (ROS) production. In contrast, a close analog (1,4-dithiane) was unable to activate neutrophil ROS production. Although 1,3-dithiane-1-oxide also stimulated neutrophil ROS production, only traces of this oxidation product were generated after a 5 h treatment of HL60 cells with 1,3-dithiane. Evaluation of several phosphatidylinositol-3 kinase (PI3K) inhibitors with different subtype specificities (A-66, TGX 221, AS605240, and PI 3065) showed that the PI3K p110δ inhibitor PI 3065 was the most potent inhibitor of 1,3-dithiane-induced neutrophil ROS production. Furthermore, 1,3-dithiane enhanced the phosphorylation of extracellular signal-regulated kinase 1/2 (ERK1/2), glycogen synthase kinase 3 α/β (GSK-3α/β), and cAMP response element binding (CREB) protein in differentiated neutrophil-like HL60 cells. Density functional theory (DFT) calculations confirmed the reactivity of 1,3-dithiane vs. 1,4-dithiane, based on the frontier molecular orbital analysis. Our results demonstrate that certain organosulfur compounds can activate neutrophil functional activity and may serve as biological response modifiers by augmenting phagocyte functions.

Inhibition of Heterocyclic Aromatic Amine Formation in Fried Ground Beef Patties by Garlic and Selected Garlic-Related Sulfur Compounds

2002 ◽  
Vol 65 (11) ◽  
pp. 1766-1770 ◽  
Author(s):  
HAN-SEUNG SHIN ◽  
W. JOHN RODGERS ◽  
ENAYAT A. GOMAA ◽  
GALE M. STRASBURG ◽  
J. IAN GRAY
Keyword(s):  
Ground Beef ◽  
Sulfur Compounds ◽  
Heterocyclic Aromatic Amines ◽  
Diallyl Disulfide ◽  
Organosulfur Compounds ◽  
Volatile Sulfur Compounds ◽  
Beef Patties ◽  
Dipropyl Disulfide ◽  
Allyl Mercaptan ◽  
Volatile Sulfur

The effects of garlic and selected organosulfur compounds (diallyl disulfide, dipropyl disulfide, diallyl sulfide, allyl methyl sulfide, allyl mercaptan, cysteine, and cystine) on the formation of heterocyclic aromatic amines (HAAs) in fried ground beef patties were evaluated. Minced garlic cloves (ca. 4.8 to 16.7%, wt/wt) or organosulfur compounds (0.67 mmol) were added directly to ground beef. Patties (100 g) were fried at 225°C (surface temperature) for 10 min per side. Two patties were fried for each replication, and five replicates were analyzed for each treatment. For each replicate, four subsamples were analyzed (two unspiked subsamples for concentration and two spiked subsamples for the recovery of HAA standards). The volatile sulfur compounds significantly (P < 0.05) reduced concentrations of 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine by reductions of 46 to 81%, while average reductions of 35, 22, and 71%, were achieved with cystine, cysteine, and whole garlic, respectively. The volatile sulfur compounds reduced concentrations of 2-amino-3,8-dimethylimidazo [4,5-f] quinoxaline by 34 to 67%, while reductions of 25, 19, and 63% (P < 0.05) were achieved with cystine, cysteine, and whole garlic, respectively. These studies confirm that garlic and some organosulfur compounds have the potential to reduce HAA formation in cooked beef patties.

A Density Functional Theory Study on the Ring-Opening Polymerization of D-Lactide Catalyzed by a Bifunctional-Thiourea Catalyst

2009 ◽  
Vol 62 (2) ◽  
pp. 157 ◽  
Author(s):  
Rong-Xiu Zhu ◽  
Ruo-Xi Wang ◽  
Dong-Ju Zhang ◽  
Cheng-Bu Liu
Keyword(s):  
Density Functional Theory ◽  
Ring Opening ◽  
Density Functional ◽  
Population Analysis ◽  
Density Functional Theory Calculations ◽  
Ring Opening Polymerization ◽  
Acyl Transfer ◽  
Frontier Molecular Orbital ◽  
Functional Theory ◽  
Elimination Pathway

The thiourea-catalyzed methanolysis of d-lactide, a model system for the initiation and propagation of the organocatalyzed ring-opening polymerization (ROP) of lactide, has been studied by performing density functional theory calculations. Both the catalyzed and uncatalyzed reactions are explored along two possible pathways: one involves the stepwise addition–elimination pathway and the other is related to the concerted pathway. It is found that the reaction without the presence of the catalyst is difficult because the barrier involved is as high as 176 kJ mol–1. With the aid of a thiourea catalyst, the barrier is reduced to 88 kJ mol–1 with a preference for the stepwise addition–elimination mechanism over the concerted one. The role of the catalyst has been rationalized by analyzing the frontier molecular orbital interactions between the catalyst and substrates and by performing natural population analysis. Finally, another mechanism involving acyl transfer is discussed for the thiourea-catalyzed ROP.

scholarly journals Chemical Composition and Immunomodulatory Activity of Essential Oils from Rhododendron albiflorum

Molecules ◽  
2021 ◽  
Vol 26 (12) ◽  
pp. 3652
Author(s):  
Igor A. Schepetkin ◽  
Gulmira Özek ◽  
Temel Özek ◽  
Liliya N. Kirpotina ◽  
Andrei I. Khlebnikov ◽  
...  
Keyword(s):  
Chemical Composition ◽  
Essential Oils ◽  
Neutrophil Migration ◽  
Compositional Analysis ◽  
Microglial Cells ◽  
Formyl Peptide Receptor ◽  
Human Neutrophils ◽  
Immunomodulatory Activity ◽  
Hl60 Cells ◽  
Formyl Peptide

Rhododendron (Ericaceae) extracts contain flavonoids, chromones, terpenoids, steroids, and essential oils and are used in traditional ethnobotanical medicine. However, little is known about the immunomodulatory activity of essential oils isolated from these plants. Thus, we isolated essential oils from the flowers and leaves of R. albiflorum (cascade azalea) and analyzed their chemical composition and innate immunomodulatory activity. Compositional analysis of flower (REOFl) versus leaf (REOLv) essential oils revealed significant differences. REOFl was comprised mainly of monoterpenes (92%), whereas sesquiterpenes were found in relatively low amounts. In contrast, REOLv was primarily composed of sesquiterpenes (90.9%), with a small number of monoterpenes. REOLv and its primary sesquiterpenes (viridiflorol, spathulenol, curzerene, and germacrone) induced intracellular Ca2+ mobilization in human neutrophils, C20 microglial cells, and HL60 cells transfected with N-formyl peptide receptor 1 (FPR1) or FPR2. On the other hand, pretreatment with these essential oils or component compounds inhibited agonist-induced Ca2+ mobilization and chemotaxis in human neutrophils and agonist-induced Ca2+ mobilization in microglial cells and FPR-transfected HL60 cells, indicating that the direct effect of these compounds on [Ca2+]i desensitized the cells to subsequent agonist activation. Reverse pharmacophore mapping suggested several potential kinase targets for these compounds; however, these targets were not supported by kinase binding assays. Our results provide a cellular and molecular basis to explain at least part of the beneficial immunotherapeutic properties of the R. albiflorum essential oils and suggest that essential oils from leaves of this plant may be effective in modulating some innate immune responses, possibly by inhibition of neutrophil migration.

Theoretical investigation on tautomerism and NLO properties of Salicylideneaniline derivatives

2021 ◽  
Author(s):  
N. Daho ◽  
N. Benhalima ◽  
F. KHELFAOUI ◽  
O. SADOUKI ◽  
M. Elkeurti ◽  
...  
Keyword(s):  
Optical Properties ◽  
Density Functional ◽  
Energy Gap ◽  
Intramolecular Proton Transfer ◽  
Basis Set ◽  
Frontier Molecular Orbital ◽  
Molecular Orbital Calculations ◽  
Visible Absorption ◽  
Charge Delocalization ◽  
Intramolecular Hydrogen

In this work, a comprehensive investigation of the salicylideneaniline derivatives is carried out using density functional theory to determine their linear and non-linear optical properties. Geometry optimizations, for gas and solvent phases, of the tautomers (enol and keto forms) are calculated using B3LYP levels with 6–31G (d,p) basis set . An intramolecular proton transfer, for 1SA-E and 2SA-E, is performed by a PES scan process at the B3LYP/6-31G (d,p) level. The optical properties are determined and show that they have extremely high nonlinear optical properties. In addition, the RDG analysis, MEP, and gap energy are calculated. The low energy gap value indicates the possibility of intramolecular charge transfer. The frontier molecular orbital calculations clearly show the inverse relationship of HOMO–LUMO gap with the first-order hyperpolarizability (β = 59.6471 × 10-30 esu), confirming that the salicylideneaniline derivatives can be used as attractive future NLO materials. Therefore, the reactive sites are predicted using MEP and the visible absorption maxima are analyzed using a theoretical UV–Vis spectrum. Natural bond orbitals are used to investigate the stability, charge delocalization, and intramolecular hydrogen bond.

scholarly journals Theoretical Study of Solvent Effects on the Electronic and Thermodynamic Properties of Tetrathiafulvalene (TTF) Molecule Based on DFT

2021 ◽  
pp. 42-54
Author(s):  
Rabiu Nuhu Muhammad ◽  
N. M. Mahraz ◽  
A. S Gidado ◽  
A. Musa
Keyword(s):  
Thermodynamic Properties ◽  
Bond Length ◽  
Density Functional ◽  
Theoretical Study ◽  
Energy Gap ◽  
Basis Set ◽  
Basis Sets ◽  
Frontier Molecular Orbital ◽  
Orbital Energy ◽  
Chemical Hardness

Tetrathiafulvalene () is an organosulfur compound used in the production of molecular devices such as switches, sensors, nonlinear optical devices and rectifiers. In this work, a theoretical study on the effects of solvent on TTF molecule was investigated and reported based on Density Functional Theory (DFT) as implemented in Gaussian 03 package using B3LYP/6-31++G(d,p) basis set. Different solvents were introduced as a bridge to investigate their effects on the electronic structure. The HUMO, LUMO, energy gap, global chemical index, thermodynamic properties, NLO and DOS analysis of the TTF molecule in order to determine the reactivity and stability of the molecule were obtained. The results obtained showed that the solvents have effects on the electronic and non-linear-optical properties of the molecule. The optimized bond length revealed that the molecule has strong bond in gas phase with smallest bond length of about 1.0834Å than in the rest of the solvents. It was observed that the molecule is more stable in acetonitrile with HOMO-LUMO gap and chemical hardness of 3.6373eV and 1.8187eV respectively. This indicates that the energy gap and chemical hardness of TTF molecule increases with the increase in polarity and dielectric constant of the solvents. The computed results agreed with the results in the literature. The thermodynamics and NLO properties calculation also indicated that TTF molecule has highest value of specific heat capacity (Cv), total dipole moment () and first order hyperpolarizability () in acetonitrile, while acetone has the highest value of entropy and toluene has a slightly higher value of zero point vibrational energy (ZPVE) than the rest of the solvents. The results show that careful selection of the solvents and basis sets can tune the frontier molecular orbital energy gap of the molecule and can be used for molecular device applications.

scholarly journals Synthesis, Crystal Structure, DFT studies, Docking Studies and Fluorescent Properties of 2-(Adamantan-1-yl)-2H-isoindole-1-carbonitrile

2018 ◽  
Author(s):  
Jacques Joubert
Keyword(s):  
Crystal Structure ◽  
Binding Affinity ◽  
Active Site ◽  
Density Functional ◽  
Protein Crystal ◽  
Frontier Molecular Orbital ◽  
Biological Interactions ◽  
Fluorescent Properties ◽  
Orthorhombic Space Group ◽  
Cell Parameters

2-(Adamantan-1-yl)-2H-isoindole-1-carbonitrile (1) has been identified as a neurobiological fluorescent ligand that may be used to develop receptor and enzyme binding affinity assays. Compound 1 was synthesised using an optimised microwave irradiation reaction and crystallised from ethanol. Crystallization occurred in the orthorhombic space group P212121 with unit cell parameters: a = 6.4487(12) Å, b = 13.648(3) Å, c = 16.571(3) Å, V = 1458(5) Å3, Z = 4. Density functional theory (DFT) (B3LYP/6-311++G (d,p)) calculations of 1 were carried out. Results showed that the optimised geometry is similar to the crystal structure parameters with a root-mean-squared deviation of 0.143 Å. Frontier molecular orbital energies and net atomic charges are discussed with a focus on potential biological interactions. Docking experiments within the active site of the neuronal nitric oxide synthase (nNOS) protein crystal structure were carried out and analysed. Important binding interactions between the DFT optimised structure and amino acids within the nNOS active site were identified that explain the strong NOS binding affinity reported. Fluorescent properties of 1 were studied using aprotic solvents of different polarities. Compound 1 showed the highest fluorescence intensity in polar solvents with excitation and emission values of 336 nm and 380 nm, respectively.

Radioprotective Activity of Naturally Occurring Organosulfur Compounds

2006 ◽  
Vol 92 (2) ◽  
pp. 163-169 ◽  
Author(s):  
Manesh Chittezhath ◽  
Girija Kuttan
Keyword(s):  
Intestinal Mucosa ◽  
Lipid Peroxides ◽  
Allyl Isothiocyanate ◽  
Sulfur Compounds ◽  
Whole Body ◽  
Phenyl Isothiocyanate ◽  
Histopathological Analysis ◽  
Diallyl Disulfide ◽  
Organosulfur Compounds ◽  
Naturally Occurring

The radioprotective effects of naturally occurring sulfur compounds and isothiocyanates such as diallyl sulfide (DAS), diallyl disulfide (DADS), allyl methyl sulfide (AMS), allyl isothiocyanate (AITC) and phenyl isothiocyanate (PITC) have been investigated in whole body irradiated Swiss albino mice. Administration of these sulfur compounds could reduce the serum content of alkaline phosphatase (ALP), which was elevated after irradiation (23.9 ± 1.82 KA units). The elevated liver content of glutamate pyruvate transaminase (GPT) in control animals (76.2 ± 2.2 U/mL) after irradiation was significantly reduced in DAS (58.93 ± 4 U/mL) and AMS (55.7 ± 2.2 U/mL) treated animals. Elevated levels of lipid peroxides in serum and liver of irradiated control animals were also significantly reduced by treatment with these sulfur compounds. The glutathione (GSH) content in liver and intestinal mucosa was drastically reduced after irradiation. All the sulfur compounds and isothiocyanates could effectively enhance the GSH content of intestinal mucosa and liver. Findings at histopathological analysis of the intestine proved to be correlated with the above results.

scholarly journals Structure, electronic properties, NBO, NLO and chemi-cal reactivity of bis (1, 4-dithiafulvalene) derivatives: functional density theory study

2017 ◽  
Vol 6 (1) ◽  
pp. 18
Author(s):  
Tahar Abbaz ◽  
Amel Bendjeddou ◽  
Didier Villemin
Keyword(s):  
Electronic Properties ◽  
Density Functional ◽  
Computational Study ◽  
Molecular Geometry ◽  
Basis Set ◽  
Frontier Molecular Orbital ◽  
Reactivity Descriptors ◽  
Nlo Property ◽  
Functional Density Theory ◽  
Nucleophilic Reactivity

In this work, through computational study based on density functional theory (DFT/B3LYP) using basis set 6-31G (d,p) a number of global and local reactivity descriptors for a series of molecules containing a TTF function which are bis (1,4-dithiafulvalene) derivatives. They were computed to predict the reactivity and the reactive sites on the molecules. The molecular geometry and the electronic properties in the ground state such as frontier molecular orbital (HOMO and LUMO), ionization potential (I) and electron affinity (A) were investigated to get a better insight of the molecular properties. Molecular electrostatic potential (MEP) for all compounds were determined to check their electrophilic or nucleophilic reactivity. Fukui index, polarizability, hyperpolarizability, second order NLO property and natural bond orbital (NBO) analyses have also employed to determine the reactivity of bis (1,4-dithiafulvalene) derivatives.

DFT/TDDFT STUDY ON DNA-BINDING AND SPECTRAL PROPERTIES OF "LIGHT SWITCH" COMPLEX [Ru(phen)2 (taptp)]2+ IN AQUEOUS SOLUTION

2008 ◽  
Vol 07 (06) ◽  
pp. 1147-1158 ◽  
Author(s):  
JUN LI ◽  
LIAN-CAI XU ◽  
SI-YAN LIAO ◽  
KANG-CHENG ZHENG ◽  
LIANG-NIAN JI
Keyword(s):  
Aqueous Solution ◽  
Dna Binding ◽  
Solvent Effect ◽  
Spectral Properties ◽  
Density Functional ◽  
Frontier Molecular Orbital ◽  
Base Pairs ◽  
Dna Base ◽  
Dna Base Pairs ◽  
Planar Area

The theoretical studies on the electronic structure, DNA-binding, and absorption-spectral properties of "light switch" complex [ Ru ( phen )2( taptp )]2+ (phen = 1,10-phenanthroline; taptp = 4,5,9,18-tetraazaphenanthreno-[9,10-b]triphenylene) in aqueous solution have been carried out using density functional theory (DFT) and time-dependent DFT (TDDFT) methods. The results show the following: (i) The solvent effect makes all the frontier molecular orbital energies of complex to increase to a certain extent; however, the energies (ε LUMO + x) of some frontier unoccupied molecular orbitals (MOs) in aqueous solution are still negative and rather lower than those of the energies (ε HOMO - x) of some frontier-occupied MOs of DNA-base pairs, and thus the complex in aqueous solution is still an excellent electron-acceptor in its DNA-binding. (ii) The solvent effect further shows that simply increasing the conjugative planar area of intercalative ligand may be ineffective on the improvement of DNA-binding of the resulting complex because of going along with the increase in the LUMO (and LUMO + x) energy. It is the reason why the DNA-binding affinity of "light switch" complex [ Ru ( phen )2( taptp )]2+ is not better than that of the well-known complex [ Ru ( phen )2( dppz )]2+ yet. (iii) The three main experimental bands (~450 nm, ~360 nm, and ~290 nm) of the studied complex in aqueous solution were further well calculated, simulated, and explained by the TDDFT computations.

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