Utility of Hydrazinopiperidinomethanethione in Synthesis of Thiadiazole,Thiadiazine, and Pyrazole Derivatives

Hydrazinopiperidinomethanethione 2 was prepared and reacted with active halo compounds, carbon disulfide, phenyliso-thiocyanate, ylidenenitriles, and N,S-acetyls to give thiadiazine 4–7 , thiadiazole 8–10 , and pyrazole 11,13 , 14–17 derivatives, respectively.     

Evaluation of comprehensive two-dimensional gas chromatography with flame photometric detection: Potential application for sulfur speciation in shale oil

Flame photometric detection in the sulfur channel has been evaluated for sulfur speciation and quantification in comprehensive two-dimensional gas chromatography [GC × GC-FPD(S)] for S-compound speciation in shale extracts. Signal non-linearity and potential quenching effects were reportedly major limitations of this detector for analysis of sulfur in complex matrices. However, reliable linear relationships with correlation coefficient >0.99 can be obtained if the sum of the square root of each modulation slice in GC × GC is plotted vs. sulfur concentration. Furthermore, the quenching effects are reduced due to essentially complete separation of S-containing components from the hydrocarbon matrix. An increase of S/N of up to 150 times has been recorded for benzothiophene and dibenzothiophene in GC × GC-FPD when compared to GC-FPD due to the modulation process. As a consequence, 10 times lower detection limits were observed in the former mode. The applicability of the method was demonstrated using shale oil sample extracts. Three sulfur classes were completely separated and the target class (thiophenes) was successfully quantified after the rest of the sample was diverted to the second detector by using a heart-cut strategy. Based on the proposed method, 70% of the sulfur in the shale oil was assigned to the thiophenes, 24% to benzothiophenes, and 5% to dibenzothiophene compounds.     

Chemical oxidative polymerization of m-phenylenediamine and its derivatives using aluminium triflate as a co-catalyst

Aromatic diamine monomers, including m-phenylenediamine (mPD), 2-methyl-m-phenylenediamine (2Me-mPD), 4-methyl-m-phenylenediamine (4Me-mPD) and trimethyl-m-phenylenediamine (tMe-mPD), were polymerized by chemical oxidation using ammonium persulfate as an oxidant. Aluminium triflate (Al(OTf)₃) was also used for the first time as a co-catalyst under various polymerization conditions. The polymerization yield was improved when Al(OTf)₃ was introduced to the polymerization reaction for most polymers. The poly(2-methyl-m-phenylenediamine) (P(2Me-mPD)), poly(4-methyl-m-phenylenediamine) (P(4Me-mPD)) and poly(trimethyl-m-phenylenediamine) (P(tMe-mPD)) polymers exhibited better solubility than poly(m-phenylenediamine) (P(mPD)) polymers in most common solvents. The homopolymers obtained were characterized by FT-IR, ¹H and ¹³C NMR, WAXD and TGA. The results showed that the yield, solubility and structure of the polymers are significantly dependent on the polymerization conditions. TGA measurements indicated that the polymers have good thermal stability and decompose above 400 °C in nitrogen.     

Application of structural analogs of dimercaptosuccinic acid-functionalized silica nanoparticles (DMSA-[silica]) to adsorption of mercury, cadmium, and lead

In order to gain additional insight into mercury selectivity with nano-sized DMSA-[silica], we investigated a series of ligands related to DMSA, these are: monomercaptosuccinic acid; MMSA, 2-mercapto-4-methyl-5-thiazoleacetic acid; MCT, ortho-thiosalicylic acid; o-TSA and para-thiosalicylic acid; p-TSA. The MMSA chelate is structurally similar to DMSA except that it has only one thiol group. The chelates o-TSA and p-TSA each have one thiol and one carboxylic acid group. MCT includes neutral S and N atoms in close proximity to the thiolate binding site. MCT, o-TSA and p-TSA resemble each other in having equal numbers of carboxylic acid and thiol groups and formation of amide bonds with the linker on silica is expected to eliminate the carboxylate binding sites, making thiolates the only binding sites for Hg(II), Cd(II), and Pb(II) metals ions in the nano-sized; MMSA-[silica], MCT-[silica], o-TSA-[silica], and p-TSA-[silica]. Each of the nano-sized MMSA-[silica], MCT-[silica], o-TSA-[silica], and p-TSA-[silica], show a higher preference for Hg(II) over Cd(II) and Pb(II) compared to the same free chelates in solution, respectively. In addition, there are differences in the level of metal ion chelation for each functionalized silica nanoparticle. These differences in the degree of metal chelation for each functionalized silica nanoparticles surface are explained by the difference in thiolate/carboxylate ratio upon attachment to the surface and on steric reasons based on the orientation of the thiol groups on the surface. When attached via amide bond formation, the thiolate site in o-TSA-[silica] will face towards the silica surface, while for p-TSA-[silica], the thiolate site is expected to be pointed outwards and away from the silica surface. In comparing MMSA-[silica] to DMSA-[silica], the thiolate/carboxylate ratio decreases from 2/1 in DMSA-[silica] to 1/1 in MMSA-[silica] (assuming attachment via one amide bond in each case). This effect of increasing the ratio of thiolate to carboxylate upon attachment to the surface is believed to play a role in the selectivity enhancement towards Hg(II) over Cd(II) and Pb(II).     

YOYO as a Dye to Track Penetration of LK15 DNA Complexes in Spheroids: Use and Limits

To elucidate the reasons underlying the poor penetration of non-viral vectors in tissues, relating transport properties to physico-chemical parameters of vectors may be crucial. These properties can be influenced by the presence of multiples labels that are used. Therefore utilizing a vector with minimum of labels preferably not more than one is important to studying penetration in tissues. The cell impermeant bisintercalating dye YOYO-1 was found suitable to both monitor the formation of complexes between DNA and an amphipathic peptide LK15 and, to track their penetration in HCT116 spheroids by confocal microscopy. The results revealed a limited decrease of fluorescence ascribed to the high affinity of YOYO-1 to bind DNA. The residual fluorescence of complexes can be exploited to monitor penetration into spheroids, after correction for YOYO-1 attenuation, and to revealing hyaluronidase-induced reduced binding. Hence high affinity dyes such as YOYO-1 with inefficiently quenched fluorescence may be important to establish a relation between novel medicines characteristics and penetration in tissues.     

Trapezoidal-Type Inequalities for Strongly Convex and Quasi-Convex Functions via Post-Quantum Calculus

In this paper, we establish new (p,q)κ1-integral and (p,q)κ2-integral identities. By employing these new identities, we establish new (p,q)κ1 and (p,q)κ2- trapezoidal integral-type inequalities through strongly convex and quasi-convex functions. Finally, some examples are given to illustrate the investigated results.     

Thiazolidinedione Derivatives: In Silico,In Vitro,In Vivo,Antioxidant and Anti-Diabetic Evaluation

This work aimed to synthesize a new antihyperglycemic thiazolidinedione based on the spectral data. The DFT\B3LYP\6-311G** level of theory was used to investigate the frontier molecular orbitals (FMOs), chemical reactivity and map the molecular electrostatic potentials (MEPs) to explain how the synthesized compounds interacted with the receptor. The molecular docking simulations into the active sites of PPAR-γ and α-amylase were performed. The in vitro potency of these compounds via α-amylase and radical scavenging were evaluated. The data revealed that compounds (4–6) have higher potency than the reference drugs. The anti-diabetic and anti-hyperlipidemic activities for thiazolidine-2,4-dione have been investigated in vivo using the alloxan-induced diabetic rat model along with the 30 days of treatment protocol. The investigated compounds didn’t show obvious reduction of blood glucose during pre-treatments compared to diabetic control, while after 30 days of treatments, the blood glucose level was lower than that of the diabetic control. Compounds (4–7) were able to regulate hyperlipidemia levels (cholesterol, triglyceride, high-density lipoproteins and low- and very-low-density lipoproteins) to nearly normal value at the 30th day.