Rapid, one-pot derivatization and distillation of chlorophenols from solid samples with their on-line enrichment

A microwave-assisted steam distillation (MASD) sample preparation technique for extracting chlorophenols from solid samples was studied. This open vessel microwave system based study developed as an integrated method since it has incorporated extractive distillation, derivatization and on-line enrichment. Gas chromatography (GC) with electron-capture detection was used for the analysis. The study involved optimization of MASD parameters and on-line enrichments using spiked solid samples. MASD achieved recoveries for spiked soil samples in the range of 94-101% within 20min with a collection of only 20ml distillate facilitating on-line enrichment. Some real samples were analyzed that included soil, wood, leather, textiles, dyes and certified reference materials of soil and wood samples. Limit of detection values of 12ng/g for pentachlorophenol and 194ng/g for monochlorophenol were found. Recoveries of 96.6% in the case of soil certified reference material (CRM) with RSD 2.7% and 80.6% in the case of wood CRM with RSD 3.3% were observed in this study. MASD studied found to produce very clean extracts in comparison to reference techniques.     

Identification and characterization of in vitro and in vivo fidarestat metabolites: Toxicity and efficacy evaluation of metabolites

The progression of diabetic complications can be prevented by inhibition of aldose reductase and fidarestat considered to be highly potent. To date, metabolites of the fidarestat, toxicity, and efficacy are unknown. Therefore, the present study on characterization of hitherto unknown in vitro and in vivo metabolites of fidarestat using liquid chromatography–electrospray ionization tandem mass spectrometry (LC/ESI/MS/MS) is undertaken. In vitro and in vivo metabolites of fidarestat have been identified and characterized by using LC/ESI/MS/MS and accurate mass measurements. To identify in vivo metabolites, plasma, urine, and feces samples were collected after oral administration of fidarestat to Sprague–Dawley rats, whereas for in vitro metabolites, fidarestat was incubated in human S9 fraction, human liver microsomes, and rat liver microsomes. Furthermore, in silico toxicity and efficacy of the identified metabolites were evaluated. Eighteen metabolites have been identified. The main in vitro phase I metabolites of fidarestat are oxidative deamination, oxidative deamination and hydroxylation, reductive defluroniation, and trihydroxylation. Phase II metabolites are methylation, acetylation, glycosylation, cysteamination, and glucuronidation. Docking studies suggest that oxidative deaminated metabolite has better docking energy and conformation that keeps consensus with fidarestat whereas the rest of the metabolites do not give satisfactory results. Aldose reductase activity has been determined for oxidative deaminated metabolite (F‐1), and it shows an IC50 value of 0.44 μM. The major metabolite, oxidative deaminated, did not show any cytotoxicity in H9C2, HEK, HEPG2, and Panc1 cell lines. However, in silico toxicity, the predication result showed toxicity in skin irritation and ocular irritancy SEV/MOD versus MLD/NON (v5.1) model for fidarestat and its all metabolites. In drug discovery and development research, it is distinctly the case that the potential for pharmacologically active metabolites must be considered. Thus, the active metabolites of fidarestat may have an advantage as drug candidates as many drugs were initially observed as metabolites.     

DFT Study of Polymorphism in Al(OH)3: A Structural Synthon Approach

All the known polymorphs of Al(OH)₃ comprise a stacking of charge neutral layers having the composition [Al_2/3□_1/3(OH)₂] (□: cation vacancy) and designated by the symbol P. Employing a single Al(OH)₃ layer (layer group p12₁/a1) as a structural synthon, the energy profile computed for the translations of P and $\bar{P}$ ($\bar{P}$ : mirror image of P) layers relative to each other within a bilayer model, not only show minima corresponding to the four known polymorphs of Al(OH)₃ but also predict three new polymorphs with energy minima at the stacking vectors (7/10, 5/18, 1) (polymorph B1), (1/2, 0, 1) (polymorph B2) and (2/5, 1/9, 1) (polymorph B4). Of these B1 and B2 are 0.30 eV and 0.23 eV below the energy of bayerite (B3), but 0.30 eV and 0.37 eV above the global minimum which corresponds to gibbsite. B4 is only 0.08 eV above the energy of bayerite. This quantitative structural synthon approach offers B1, B2, and B4 as legitimate targets for future synthetic efforts.     

Synthesis, Structure and Physical Properties of a Barium（II） Complex with 5-Sulfoisophthalic Acid Sodium

An alkaline earth metal-organic framework [Ba(Hsip)(H2O)4]n (1, NaH2sip = 5-sulfoisophthalic acid sodium) has been constructed, and characterized by single-crystal X-ray diffraction. In complex 1, each Ba(II) atom coordinates to one ligand Hsip3- and four water molecules with a distorted nine-coordinated monocapped tetragonal antiprism geometry. Each Hsip2- anion acts as a μ3-bridging ligand, in which two carboxylate groups adopt the same bidentate chelating coordinating model and the sulfonate group takes a monodentate coordinating model, resulting in a wave-like two-dimensional network with a (6, 3) topological structure. The two-dimensional networks are further linked by O-H···O to form a three-dimensional structure. Luminescent property and thermal stability of complex 1 are investigated. 1 belongs to the orthorhombic system, space group Pna21 with a = 7.3333(2), b = 16.7044(3), c = 10.4817(2), Z = 4, V = 1283.99(5)3, Mr = 453.58, Dc = 2.346 g/cm3, F(000) = 880, μ = 3.314 mm-1, the final R = 0.0261 and wR = 0.0592 for 2425 observed reflections with I > 2σ(I).     

Density functional theoretical investigation of the aromatic nature of BN substituted benzene and four ring polyaromatic hydrocarbons

We have studied the topological and local aromaticity of BN-substituted benzene, pyrene, chrysene, triphenylene and tetracene molecules. The nucleus-independent chemical shielding (NICS), harmonic oscillator model of aromaticity (HOMA), para-delocalization index (PDI) and aromatic fluctuation index (FLU) have been calculated to quantify aromaticity in terms of magnetic and structural criteria. We find that charge separations due to the introduction of heteroatoms largely affect both the local and topological aromaticity of these molecules. Our studies show that the presence of any kind of heteroatom in the ring not only reduces the local delocalization in the six membered ring, but also affects strongly the topological aromaticity. In fact, the relative orders of the topological and local aromaticity depend strongly on the position of the heteroatoms in the structure. In general, more ring shared BN containing molecules are less aromatic than the less ring shared BN molecules. In addition our results provide evidence that the structural stability of the molecule is dominated by the σ bond rather than the π bond.     

Thermal decomposition kinetics of potassium iodate

The thermal decomposition of potassium iodate (KIO₃) has been studied by both non-isothermal and isothermal thermogravimetry (TG). The non-isothermal simultaneous TG–differential thermal analysis (DTA) of the thermal decomposition of KIO₃ was carried out in nitrogen atmosphere at different heating rates. The isothermal decomposition of KIO₃ was studied using TG at different temperatures in the range 790–805 K in nitrogen atmosphere. The theoretical and experimental mass loss data are in good agreement for the thermal decomposition of KIO₃. The non-isothermal decomposition of KIO₃ was subjected to kinetic analyses by model-free approach, which is based on the isoconversional principle. The isothermal decomposition of KIO₃ was subjected to both conventional (model fitting) and model-free (isoconversional) methods. It has been observed that the activation energy values obtained from all these methods agree well. Isothermal model fitting analysis shows that the thermal decomposition kinetics of KIO₃ can be best described by the contracting cube equation.     

DEM investigation of mixing indices in a ribbon mixer

Mixing index is an important parameter to understand and assess the mixing state in various mixers including ribbon mixers,the typical food processing devices.M...     

Effect of spatial heterogeneity on level of rejuvenation in Ni80P20 metallic glass

Understanding the relation between spatial heterogeneity and structural rejuvenation is one of the hottest topics in the field of metallic glasses (MGs). In this work, molecular dynamics (MD) simulation is implemented to discover the effects of initial spatial heterogeneity on the level of rejuvenation in the Ni$_{80}$P$_{20 }$MGs. For this purpose, the samples are prepared with cooling rates of $10^{10}$ K/s-$10^{12}$ K/s to make glassy alloys with different atomic configurations. Firstly, it is found that the increase in the cooling rate leads the Gaussian-type shear modulus distribution to widen, indicating the aggregations in both elastically soft and hard regions. After the primary evaluations, the elastostatic loading is also used to transform structural rejuvenation into the atomic configurations. The results indicate that the sample with intermediate structural heterogeneity prepared with 10$^{11}$ K/s exhibits the maximum structural rejuvenation which is due to the fact that the atomic configuration in an intermediate structure contains more potential sites for generating the maximum atomic rearrangement and loosely packed regions under an external excitation. The features of atomic rearrangement and structural changes under the rejuvenation process are discussed in detail.     

Focused microwave aqueous extraction of chlorophenols from solid matrices and their analysis by chromatographic techniques

Open-vessel focused microwave (FMW) extraction with a purely aqueous carbonate solution was used for the extraction of chlorophenols from various solid matrices. After SPE on C18-bonded silica, the analytes were determined as such by LC-UV or, as their acetyl derivatives, by GC-ECD. The FMW aqueous extraction is efficient and rapid and no organic solvents are used. PCP was detected in several solid samples, with recoveries of 101-115% (RSD, 2-4%) relative to Soxhlet extraction. Similar recoveries were obtained for the other chlorophenols for spiked samples.