AgNOR increase in buccal epithelial cells of trisomy 21 infants

The aim of this study is to compare the Argilophilic Nucleolus Organizer Regions (AgNORs) level between Down syndrome (DS) patients and controls in a tissue sharing the same embryonic origin with the central nervous system and compare the results with those obtained recently by us from DS's lymphocytes. For this, buccal desquamating epithelial cells well known as the ectodermic origin were used. Since the AgNOR staining intensity is an indicator of the ribosomes biosynthesis rate, comparison of the image analysis values of the AgNOR area/total nuclear area (NORa/TNa) in buccal desquamating epithelial cells of DS patients and controls provided a plausible conclusion about the regulation/deregulation of the rRNA genes (rDNA) in these cells of DS babies/infants. The (NORa/TNa) proportion was calculated using an in-house computer program. Fifty buccal desquamating cells were analysed for each individual to determine the average NORa/TNa value per individual. In contrast to healthy controls, NORa/TNa proportion value of buccal epithelial cells from DS patients found significantly higher than that of the controls: (4.08 ± 1.16)% and (2.13 ± 0.55)%, respectively. This 92% increase is far higher than the expected value due to the extra rRNA genes on the extra-chromosome 21. Finally DS babies/infants exhibit very higher AgNOR expression increase in their buccal epithelial cells compared to controls. This is the first study that is available on the comparison of AgNOR expression levels in buccal epithelial cells between DS infants and their controls.     

Biological activities,phenolic profiles and essential oil components of Tanacetum cilicicum (BOISS.) GRIERSON

Tanacetum species are consumed as tea in Turkey. We comparatively evaluated the phytochemical potentials and antioxidant activities of the essential oil and methanolic extracts of Tanacetum cilicicum. The chemical constitutes of T. cilicicum essential oil and antioxidant activity of this species was analysed by gas chromatography–mass spectrometry (GC–MS) method. Bicyclo (3,1,1) hept-2-en-4-ol (21.92%), camphor (15.56%) and 1,8-cineole (13.45%) which are oxygenated monoterpenes were found as the major constituents. Phenolic acids and flavonoids were quantificated by HPLC–UV. Catechin was found as the main component. The essential oils and methanolic extracts were evaluated by antioxidant activities. The leaves exhibited significant metal chelation activity with a value of 20.75 ± 4.63 μg/mL.     

Synthesis of new chiral calix[4]azacrowns for enantiomeric recognition of carboxylic acids

Two novel chiral calix[4]azacrown ethers 4 and 5 bearing a furfuryl group on the nitrogen atom were developed by the reaction of dibromo- or ditosyl derivatives of p-tert-butylcalix[4]arenes 2 and 3 with a chiral diol, 1. The enantioselective recognition of these receptors towards the enantiomers of racemic carboxylic acids has been studied by ¹H NMR spectroscopy. The molar ratio and the association constants of the chiral compounds 4 and 5 with each of the enantiomers of guest molecules were determined by using Job plots and a nonlinear least-squares fitting method, respectively. The Job plots indicate that both of the hosts form 1:1 instantaneous complexes with (R)- or (S)-mandelic acid and (l)- or (d)-dibenzoyltartaric acid. The receptors exhibited different chiral recognition abilities towards the enantiomers of racemic guests.     

Efficient and selective synthesis of quinoline derivatives

The bromination reaction of 1,2,3,4-tetrahydroquinoline (7) was investigated by NBS and molecular bromine. One-pot synthesis is described for synthetically valuable 4,6,8-tribromoquinoline (3) and 6,8-dibromo-1,2,3,4-tetrahydroquinoline (6) on bromination of 1,2,3,4-tetrahydroquinoline (7) in efficient yields (75 and 90%, respectively). 6-Bromo- (4) and 6,8-dibromo-1,2,3,4-tetrahydroquinolines (6) were converted to 6-bromo- (1) and 6,8-dibromo quinolines (2), respectively, by aromatization with DDQ in 83 and 77% yields, respectively. Several novel trisubstituted quinoline derivatives were efficiently prepared via lithium-halogen exchange reactions of tribromide 3. Treatment of 4,6,8-tribromoquinoline with BuLi followed by quenching with electrophiles [Si(CH₃)₃Cl, S₂(CH₃)₂, I₂] regioselectively proceeded at C-4 and C-8 sites and afforded corresponding 4,8-disubstituted-6-bromoquinolines. Similarly, lithiation of tribromide 3 followed by addition of water to the intermediate produced 6-bromoquinoline in 65% yield. Copper-induced nucleophilic substitution of tribromide 3 with NaOMe afforded 4,6,8-trimethoxyquinoline (17) in 60% yield.     

Description of Barely Transitive Groups with Soluble Point Stabilizer

We consider a ring whose left modules of finite length are semisimple and prove some results on such a ring. We also consider when such a ring is a left V-ring.     

Chiral calix[4]azacrowns for enantiomeric recognition of amino acid derivatives

In this study the synthesis of novel chiral calix[4]azacrown derivatives has been reported. The enantioselectivity of chiral receptors was investigated by using UV-vis spectroscopy. All the chiral calix[4]arene derivatives exhibited certain chiral recognition toward the enantiomers of phenylalanine (Phe-OMe·HCl) and alanine methyl ester hydrochlorides (Ala-OMe·HCl). As a chiral receptor, the furfuryl-armed calix[4]azacrown ether 7 has the best enantiomeric discriminating ability for α-amino acid ester hydrochlorides (up to K_L/K_D=2.08, ΔΔG₀=−1.82 kJ mol⁻¹) in CHCl₃. The enantiomeric recognition abilities for guests are also discussed from a thermodynamic point of view.     

Kinetic and mechanistic features of carbon dioxide reforming of methane over Co–Ce/ZrO2 catalysts

Carbon dioxide reforming of methane (CDRM) is an effective route to utilize CO₂ and CH₄, the most abundant, thermodynamically stable and hazardous greenhouse gases. To overcome the economical impediments to favor CDRM's industrial applicability, its mechanistic features need to be revealed both for developing efficient catalysts and optimizing operational conditions. In this context, this work aims to obtain power-law type CDRM kinetic expressions over 5%Co–2%Ce/ZrO₂ and 10%Co–2%Ce/ZrO₂ catalysts and compare and analyze mechanistic routes to elucidate the effect of the Co:Ce ratio on kinetics. The empirical power-law type rate expressions were estimated with the reaction orders of 1.63 and 1.12 for CH₄ and 0.29 and –0.12 for CO₂ for 5%Co–2%Ce/ZrO₂ and 10%Co–2%Ce/ZrO₂ catalysts, respectively. Limited CH₄ activation and, thus, carbon formation due to low Co loading lead to accumulation of surface oxygen on ZrO₂ as redox ability of Ce becomes suppressed. This causes higher CO₂ activation barrier. The presence of H₂ in the feed slows down mechanistic steps involving CH_x. The reactions including CH₄ activation, most probably reversible direct CH₄ dissociation, are found to be rate determining.     

Arene ruthenium metallacycles containing chelating thioamide ligands

Cationic, chiral arene ruthenium complexes of the type [Ru(η⁶-cym)(PPh₃){κ²N,S-PhNC(S)R}]BPh₄ were prepared in high yields by refluxing a mixture containing [(η⁶-cym)RuCl₂]₂, Ph₃P, PhNHC(S)R, NaBPh₄ and Et₃N in MeOH. A series of seven complexes with different thioamide ligands was prepared and fully characterised by spectroscopic methods including NMR spectroscopy and electrospray mass spectrometry. The solid-state structures of two complexes were determined by single crystal X-ray diffraction.     

Azatruxene-Based,Dumbbell-Shaped,Donor–π-Bridge–Donor Hole-Transporting Materials for Perovskite Solar Cells

Three novel donor–π-bridge–donor (D -π-D) hole-transporting materials (HTMs) featuring triazatruxene electron-donating units bridged by different 3,4-ethylenedioxythiophene (EDOT) π-conjugated linkers have been synthesized, characterized, and implemented in mesoporous perovskite solar cells (PSCs). The optoelectronic properties of the new dumbbell-shaped derivatives (DTTXs) are highly influenced by the chemical structure of the EDOT-based linker. Red-shifted absorption and emission and a stronger donor ability were observed in passing from DTTX-1 to DTTX-2 due to the extended π-conjugation. DTTX-3 featured an intramolecular charge transfer between the external triazatruxene units and the azomethine–EDOT central scaffold, resulting in a more pronounced redshift. The three new derivatives have been tested in combination with the state-of-the-art triple-cation perovskite [(FAPbI₃)_0.87(MAPbBr₃)_0.13]_0.92[CsPbI₃]_0.08 in standard mesoporous PSCs. Remarkable power conversion efficiencies of 17.48 % and 18.30 % were measured for DTTX-1 and DTTX-2 , respectively, close to that measured for the benchmarking HTM spiro-OMeTAD (18.92 %), under 100 mA cm⁻² AM 1.5G solar illumination. PSCs with DTTX-3 reached a PCE value of 12.68 %, which is attributed to the poorer film formation in comparison to DTTX-1 and DTTX-2 . These PCE values are in perfect agreement with the conductivity and hole mobility values determined for the new compounds and spiro-OMeTAD. Steady-state photoluminescence further confirmed the potential of DTTX-1 and DTTX-2 for hole-transport applications as an alternative to spiro-OMeTAD.