Determination of polycyclic aromatic hydrocarbons in environmental samples by high performance thin-layer chromatography and fluorescence scanning densitometry

High performance thin-layer chromatography (HPTLC) with fluorescence scanning densitometry was used for the quantitative determination of polycyclic aromatic hydrocarbons in the soluble organic fraction of air particulate samples. A method using normalized emission response ratios was developed to determine sample identity and to test for peak homogeneity. To preserve the high sample throughput of HPTLC, the two-point calibration method was used for quantitation. The principal advantages of HPTLC as a screening technique for environmental samples are its low cost, methodological simplicity, high sample throughput, and the ability to analyze crude samples with a minimum amount of sample cleanup.     

Quaternary ammonium compounds in roots and leaves of Capparis spinosa L. from Saudi Arabia and Italy: investigation by HPLC-MS and 1H NMR

Capparis spinosa L. is a perennial plant typical of the Mediterranean flora and a multipurpose plant used for curing various human ailments. Quaternary ammonium compounds (QACs), as constituents of Capparaceae, play important roles in protecting against abiotic stress. Aim of this work was to determine QACs in root and leaves of caper from two proveniences. The presence of stachydrine, choline, glycine betaine and homo-stachydrine has been confirmed by high resolution MS, while ¹H NMR was applied to quantify the main QACs in the aqueous extracts. Stachydrine was quantified at 20.2 mg/g and 32.3 mg/g on dry leaves from South of Italy and Saudi Arabia, respectively, while a minor content was in dry roots (from 10.4 to 12.5 mg/g). Choline was considerably lower both in leaves and roots (from 0.3 to 1.2 mg/g). To our knowledge, this is the first report on the determination of QACs both in root and leaves of C. spinosa.     

Medicinal Potential of Isoflavonoids: Polyphenols That May Cure Diabetes

In recent years, there is emerging evidence that isoflavonoids, either dietary or obtained from traditional medicinal plants, could play an important role as a supplementary drug in the management of type 2 diabetes mellitus (T2DM) due to their reported pronounced biological effects in relation to multiple metabolic factors associated with diabetes. Hence, in this regard, we have comprehensively reviewed the potential biological effects of isoflavonoids, particularly biochanin A, genistein, daidzein, glycitein, and formononetin on metabolic disorders and long-term complications induced by T2DM in order to understand whether they can be future candidates as a safe antidiabetic agent. Based on in-depth in vitro and in vivo studies evaluations, isoflavonoids have been found to activate gene expression through the stimulation of peroxisome proliferator-activated receptors (PPARs) (α, γ), modulate carbohydrate metabolism, regulate hyperglycemia, induce dyslipidemia, lessen insulin resistance, and modify adipocyte differentiation and tissue metabolism. Moreover, these natural compounds have also been found to attenuate oxidative stress through the oxidative signaling process and inflammatory mechanism. Hence, isoflavonoids have been envisioned to be able to prevent and slow down the progression of long-term diabetes complications including cardiovascular disease, nephropathy, neuropathy, and retinopathy. Further thoroughgoing investigations in human clinical studies are strongly recommended to obtain the optimum and specific dose and regimen required for supplementation with isoflavonoids and derivatives in diabetic patients.     

Phosphorus ozonides adducts

Abstract

Ozone reacts quantitatively on tricoordinated and dicoordinated Phosphorus Compounds. The oxidative addition of ozone on phosphites leads to pentacoordinated or hexacoordinated phosphorus adducts. These adducts are unstable in solution. The decomposition gives the corresponding phosphoric ester with singlet oxygen evolution. In the same conditions, ozone reacts on diphosphene and gives after double bond rupture an adduct: the metaphosphonate. The relative stabilities and oxidative properties are discussed.     

Ozonization: An Efficient Method for the Oxidation of Halophosphines

Abstract

The ozonization of various halophosphines 1a-j leads with quantitative yields to the corresponding phosphine oxides 2a-j.

Ozonization is a convenient method of oxidation, in particular of compounds with bulky ligands (1c, 1d, 1e).     

Theoretical analysis of the local orientation effect and the lift‐hyperlayer mode of rodlike particles in field‐flow fractionation

We investigated theoretically the effects of the cross‐stream migration and the local average orientation of rodlike particles on the shape‐based separation using field‐flow fractionation. The separation behavior was analyzed by comparing the retention ratios of spheres and rods. The retention ratio of a rod was evaluated through the derivation of its cross‐sectional concentration profile by considering the rod migration and the local average orientation. Our study in various flow conditions showed that the rod migration, caused by the hydrodynamic interaction with a wall, can affect the separation behavior as a lift‐hyperlayer mode. We also demonstrated that the local average orientation, which is a function of a local shear rate and a rotational diffusivity, results in the transverse diffusivity that is different from its perpendicular diffusivity. These results suggest that the experimental separation behaviors of rods in field‐flow fractionation may not be fully explained by the current theory based on the normal mode and the steric mode. We also characterized each condition where one of the normal mode, the steric mode of spheres, and the lift‐hyperlayer mode of rods is dominant.     

Electronic structure,theoretical electronic properties of tetraphenyldithiapyranylidene DIPSϕ4 molecule,and evaluation of the charge transfer occurring with doping agents like TCNQ

An extensive theoretical calculation of the tetraphenyldithiapyranylidene DIPS ?₄ molecule by means of the MSX _α method is presented. The results obtained permit one to interpret the optical spectrum and the XPS spectrum as well as the charge transfer between DIPS ?₄ and planar molecular semiconductor compounds such as TCNQ . To our knowledge, this is the first theoretical determination to date of such a charge transfer ratio from separate parameter-free calculations on large-size molecules.     

Characterization of Antioxidant Activity of Momordica Charantia Fruit by Infrared-Based Fingerprinting

Momordica charantia is widely consumed edible fruit. The food and pharmaceutical industries use it as a natural antioxidant. However, the quality control of M. charantia-based medicinal products is questionable due to the complexity of metabolites in this fruit. Hence, this study has developed a statistical model in predicting the antioxidant value through the 2, 2-diphenyl-1 picrylhydrazyl radical scavenging activity and ferric reducing antioxidant power based on infrared spectroscopy with attenuated total reflectance. This technique was reliably used for quality control. Six ethanol extracts (0, 20, 40, 60, 80, and 100% in water) of this plant’s fruit were prepared. The radical scavenging and ferric reducing antioxidant power activities were measured and the chemical profiling of the extracts was fingerprinted by infrared spectroscopy between 4,000 and 600?cm^?1 at a resolution of 4?cm^?1. Statistical analysis was developed by correlating the bioactivity and infrared spectra of each extract using orthogonal partial least square discriminant analysis. The C–N, C?O, C–O, C–H, and OH infrared signals were positively correlated with biological activity. The antioxidant activity of the fruit of M. charantia may be due to the presence of several antioxidants that work synergistically.     

Effect of radiation dose on the properties of natural rubber nanocomposite

Effect of radiation dose and carbon nanotubes (CNT) on the mechanical properties of standard Malaysian rubber (SMR) was investigated in this study. SMR nanocomposites containing 1–7 phr CNT were prepared using the solvent casting method and the nanocomposites were radiated at doses of 50–200 kGy. The change in mechanical properties, especially, tensile strength (Ts), elongation at break (Eb), hardness and tensile modulus at 100% elongation (M₁₀₀) were studied as a function of radiation dose. The structure and morphology of reinforced natural rubber was investigated by FESEM, TEM and AFM in order to gain further evidence on the radiation-induced crosslinking. It was found that the Ts, M₁₀₀ and the hardness of the SMR/CNT nanocomposites significantly increased with radiation dose; the elongation at break exhibited an increase up to 100 kGy, and a downward trend thereafter. Results on gel fraction further confirmed the crosslinking of SMR/CNT nanocomposites upon radiation.     

Structure and dynamics of highly PEG-ylated sterically stabilized micelles in aqueous media

Molecular assemblies of highly PEG-ylated phospholipids are important in many biomedical applications. We have studied sterically stabilized micelles (SSMs) of self-assembled DSPE–PEG2000 in pure water and isotonic HEPES-buffered saline solution. The observed SSM sizes of 2–15 nm largely depend on the solvent and the lipid concentration used. The critical micelle concentration of DSPE–PEG2000 is 10 times higher in water than in buffer, and the viscosity of the dispersion dramatically increases with the lipid concentration. To explain the experimentally observed results, we performed atomistic molecular dynamics simulations of solvated SSMs. Our modeling revealed that the observed assemblies have very different aggregation numbers (N(agg) ≈ 90 in saline solution and N(agg) < 8 in water) because of very different screening of their charged PO4(–) groups. We also demonstrate that the micelle cores can inflate and their coronas can fluctuate strongly, thus allowing storage and delivery of molecules with different chemistries.