Chemistry Commons^™

Spectral, Electrochemical, Luminescence, And Dye-Sensitized Solar Cell Studies Of Mono And D-F Hetero Binuclear Cryptates, Arunachalam Vijayaraj, Raju Prabu, Ranganathan Suresh, Subbaiah Manoharan, Sambandam Anandan, Vengidusamy Narayanan

Turkish Journal of Chemistry

Mono and hetero binuclear cryptates, [Gd(III)ML]^+ [M = VO(IV), Co(II), Ni(II), Cu(II)], were synthesized by a 2-step method. The ligand L represents the deprotonated anionic cryptate obtained by the 2+3 condensation of tris-(2-aminoethyl)amine with 2,6-diformyl-4-nitrophenol. The complexes were characterized by elemental analysis, spectral, magnetic, and electrochemical studies. Fluorescence of Gd(III) ion in the cavity was quenched by the encapsulated Cu(II) and Ni(II) ions. [GdCoL(NO_3)]^+ cryptate had a high lifetime value compared to other cryptates. The cyclic voltammogram showed that the reduction potential values of [Gd(M)L] M = VO(IV), Co(II), Ni(II), and Cu(II) complexes were in the following order: Cu(II) > Ni(II) …

Establishment Of An Electrochemical Rna Aptamer-Based Biosensor To Trace Nanomolar Concentrations Of Codeine, Mehdi Saberian, Davoud Asgari, Yadollah Omidi, Jaleh Barar, Hossein Hamzeiy

Turkish Journal of Chemistry

Codeine is an opium alkaloid with a great potential of abuse among opioid consumers. Detection of codeine is a routine procedure in the military and government of some countries for personnel recruitment. Therefore, a specific, selective, and easy to use method would be an important improvement in such detection procedures. According to previous reports, short single-stranded DNA or RNA sequences with high affinity and specificity to their targets, aptamers, could be used for designing an accurate and specific biosensor for codeine. This study introduces an aptamer-based biosensor for codeine detection in nanomolar concentrations by an electrochemical method, and ferrocene carboxylic …

C_2-Symmetric Chiral Diamine Ligands For Enantiomeric Recognition Of Amino Acid Esters And Mandelic Acid By Proton Nmr Titration Method, Hayri̇ye Aral, Tarik Aral, Mehmet Çolak, Berri̇n Zi̇yadanoğullari, Recep Zi̇yadanoğullari

Turkish Journal of Chemistry

Two novel C_2-symmetric chiral diamines containing \alpha -phenylethyl and \alpha -(1-naphthyl)ethyl chiral subunits were prepared with quantitative yields. Enantiomeric recognition properties of these simple structured diamine ligands towards D- and L-amino acid esters and D- and L-mandelic acid were examined by the ^1H NMR titration method. These ligands exhibited strong complexation (with K_f up to 2481 M^{-1}) and good enantioselectivity (up to K_L/K_D = 4.08) towards the mandelic acid enantiomers. The results show that simple structured and easily accessible acyclic C_2-symmetrical compounds can also be used for enantiomeric recognition of racemic amino acids and mandelic acid in addition to complex …

New Synthetic Strategy For Novel 6-Arylazo-5-Methyl-3-Aryl-Thiazolo[2,3-C]- [1,2,4]Triazoles And Study Of Their Solvatochromic Properties, Ahmad Sami Shawali, Mohie Eldin Moustafa Zayed

Turkish Journal of Chemistry

Two series of 6-arylazothiazol[2,3-c][1,2,4]triazoles were prepared via oxidative cyclization of the respective aldehyde N-(5-arylazo-4-methylthiazol-2-yl)-hydrazones. The structures of the latter hydrazone precursors and the azo compounds were confirmed by spectral and elemental analyses. The solvatochromism of the title azo dyes is evaluated by means of the Kamlet--Taft equation and discussed.

Flavonoid Constituents Of Sideritis Caesarea, Belkis Halfon, Ece Çi̇ftçi̇, Gülaçti Topçu

Turkish Journal of Chemistry

The acetone extract of the aerial parts of Sideritis caesarea Duman, Aytaç & Başer (Lamiaceae) afforded the flavonoids penduletin (1) and apigenin (2) and 6 glycosylated flavonoids, 4'-O-methyl-isoscutellarein-7-O-[6'''-O-acetyl-\beta-D-allopyranosyl- (1 \to 2)]-6\"-O-acetyl-\beta -D-glucopyranoside (3), 4'-O-methylhypolaetin- 7-O-[6'''-O-acetyl-\beta -D-allopyranosyl-(1 \to 2)]-6\"-O-acetyl-\beta- D-glucopyranoside (4), isoscutellarein-7-O-[6'''-O-acetyl-\beta- D-allopyranosyl-(1 \to 2)]-6\"-O-acetyl-\beta -D-glucopyranoside (5), isoscutellarein-7-O-[6'''-O-acetyl-\beta -D-allopyranosyl-(1 \to 2)]- \beta-D-glucopyranoside (6), 4'-O-methylhypolaetin-7-O- [6'''-O-acetyl-\beta -D-allopyranosyl-(1 \to 2)]-\beta-D- glucopyranoside (7), and hypolaetin-7-O-[6'''-O-acetyl-\beta- D-allopyranosyl-(1 \to 2)]-\beta -D-glucopyranoside (8). The compounds were identified by the use of 1D- and 2D-NMR and UV spectroscopic techniques and by comparisons with the reported data. The acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) inhibitory activities of the acetone, methanol, …

Exploring Distinct Binding Site Regions Of \Beta_2-Adrenergic Receptor Via Coarse-Grained Molecular Dynamics Simulations, Si̇bel Çakan, Ebru Demet Akdoğan

Turkish Journal of Chemistry

\beta_2-Adrenergic receptor (\beta_2AR) is a G protein- coupled receptor that is highly flexible and able to recognize a wide range of ligands through its conformational variations. Active and inactive conformations revealed by recent crystallographic experiments do not provide a complete dynamic picture of the receptor, especially in the binding site. In this study, molecular dynamics (MD) simulation through a residue-based coarse-grained model is used as an alternative and efficient method to explore a wider conformational search space. The system was composed of \beta_2AR embedded into a 1-palmitoyl-2-oleoyl-phosphatidylcholine membrane bilayer with surrounding water. A total of 6 \mu s of simulation …

Dft Study Of Tautomerism In Aklavinone, Burhan Lemi̇ Türker

Turkish Journal of Chemistry

Aklavinone has an anthraquinone-based chromophore and its backbone highly resembles the kernel of some anthracycline antibiotics that possess anticancer activity, e.g., daunomycin. Since aklavinone's structure possesses many --OH groups and 2 keto groups, it is quite probable that certain tautomeric equilibria may occur. Presently, aklavinone prototropic tautomers possessing embedded anthraquinone moiety have been investigated quantum chemically by using density functional theory at the levels of RB3LYP/6-31G(d) and RB3LYP/6-31G(d,p). Additionally, IR spectra of the tautomers were calculated. Moreover, the phenolate ions obtained from the most stable tautomer in water were considered, and the protonation of this tautomer at various possible sites …

Calixarene-Based Receptors For Molecular Recognition, Mustafa Yilmaz, Serkan Erdemi̇r

Turkish Journal of Chemistry

Calixarene-based molecular receptors have been a widely developing area in material science and technology for the last few decades. Due to their bowl-shaped geometry, calixarene macrocycles are used as hosts allowing organic and inorganic guests to coordinate/sorb onto their cavity. This work briefly reviews the recent development of calixarenes.

Synthesis Of Fused Tetrazolone Derivatives, Sevi̇l Özcan, Zeynep Ekmekçi̇, Berk Müjde, Meti̇n Balci

Turkish Journal of Chemistry

New fused tetrazolone derivatives were synthesized using homophthalic and maleic anhydrides. Treatment of anhydrides with trimethylsilyl azide opened the lactone rings and formed the corresponding intermediates, which bore 1,3-dipole and dipolarophile functionalities in ortho positions. The intermediates partially underwent internal 1,3-dipolar cycloaddition to produce fused tetrazolone derivatives. When the carbonyl groups in anhydride were not conjugated with any double bond, then a triazine-fused tetrazolone derivative was formed.

Anticholinesterase Furocoumarins From Heracleum Platytaenium, A Species Endemic To The Ida Mountains, Demet Di̇ncel, Seda Damla Hatipoğlu, Ahmet Ceyhan Gören, Gülaçti Topçu

Turkish Journal of Chemistry

The petroleum ether extract of Heracleum platytaenium afforded 8 furocoumarins (psoralen, bergapten, xanthotoxin, pimpinellin, isopimpinellin, sphondin, byakangelicin, and heraclenol) and the methanol extract of H. platytaenium gave only 1 glycosylated dihydrofurocoumarin, apterin. In addition, stigmasterol was also obtained from petroleum ether extract. Structure identification of the isolated compounds has been achieved by using spectroscopic methods, namely 1D and 2D NMR experiments and mass spectral analyses. The antioxidant activity of the extracts and pure compounds was investigated by 2 methods, including DPPH free radical scavenging activity and lipid peroxidation inhibitory activity by \beta-carotene-linoleic acid assays. The anticholinesterase activity of petroleum ether …

Synthesis Of Novel Benzimidazole Salts And Microwave-Assisted Catalytic Activity Of In Situ Generated Pd Nanoparticles From A Catalyst System Consisting Of Benzimidazol Salt, Pd(Oac)_2, And Base In A Suzuki-Miyaura Reaction, Ülkü Yilmaz, Hasan Küçükbay, Sevi̇m Türkteki̇n Çeli̇kesi̇r, Mehmet Akkurt, Orhan Büyükgüngör

Turkish Journal of Chemistry

Novel benzimidazolium salts having N-benzyl or N-(4-substitutedbenzyl) groups were synthesized and their microwave-promoted catalytic activity for the Suzuki--Miyaura cross-coupling reaction were determined using in situ formed palladium(0) nanoparticles (PdNPs) from a catalytic system consisting of Pd(OAc)_2/K2CO_3 in DMF/H_2O. PdNPs were characterized by X-ray diffraction (XRD) pattern and particle size of in situ generated PdNPs from the Pd(111) plane was determined to be of diameter 19.6 nm by the Debye--Scherrer equation. Moreover, the yield of the Suzuki--Miyaura reactions with aryl iodides and aryl bromides was found to be nearly quantitative. The synthesized benzimidazole salts (1--5) were identified by ^1H and ^{13}C …

Optimization Of A Gas Chromatography--Mass Spectrometry Method Using Chemometric Techniques For The Determination Of Ezetimibe In Human Plasma, Ebru Uçaktürk, Nuran Özaltin

Turkish Journal of Chemistry

A new, rapid, and sensitive gas chromatography--mass spectrometry (GC-MS) method was developed for the determination of ezetimibe (EZE) in human plasma. EZE was derivatized prior to GC-MS analysis. Various derivatization techniques such as acetylation, methylation, and silylation were tried. EZE was extracted from plasma with high recovery (94.39%--97.57%) using methyl tertbutyl ether and carbonate buffer (pH 9). Chromatographic conditions were optimized using chemometric methods. In the first step, optimization with factorial design, chromatographic variables (initial and final column temperature, oven ramp rate, and flow rate of gas) were screened to select important variables for the retention of EZE. In the …

Synthesis, Characterization, And Fluorescence Study Of Phthalhydrazidylazo Derivative Of An Unsaturated Diketone And Its Metal Complexes, Radhika Pallikkavil, Muhammed Basheer Ummathur, Krishnannair Krishnankutty

Turkish Journal of Chemistry

The coupling of diazotized luminol with the unsaturated diketone 1,7-diphenylhepta-4,6-diene-1,3-dione yielded a new type of tridentate ligand (H_2L). Analytical, IR, ^1H NMR, and mass spectral data indicate the existence of the compound in the intramolecularly hydrogen-bonded keto-hydrazone tautomeric form. Dibasic tridentate coordination of the compound in its [ML(H_2O)] complexes [M = Cu(II), Ni(II) and Zn(II)] was established on the basis of analytical and spectral data. The Ni(II) and Zn(II) chelates are diamagnetic while Cu(II) complex showed normal paramagnetic moment. The fluorescence maxima of the compound in different solvents show that the emission wavelength increases with increases in the polarity of …

Electrochemical Determination Of Sudan Iv In Food Samples By Using Graphene-Modified Glassy Carbon Electrodes, Meifeng Chen, Xinying Ma, Xia Li

Turkish Journal of Chemistry

A simple and sensitive modified electrode was fabricated with graphene via the drop-casting method and applied for the electrochemical detection of Sudan IV. Cyclic voltammetry (CV) was used to investigate the electrochemical behaviors of Sudan IV in phosphate buffer solution (PBS). The experimental conditions such as determining medium, scan rate, and accumulation time were optimized for the determination of Sudan IV. The sensor has excellent performance associated with high sensitivity, a low detection limit (6.00 \times 10^{-8} M), and a wide linear range of 2.00 \times 10^{-7} M to 8.00 \times 10^{-5} M with a correlation coefficient as follows: i_{pc} …

Asymmetric Henry Reaction Catalyzed By Cu(I)-Based Chiral Amino Alcohol Complex, Tianhua Shen, Quan Qin, Hang Ni, Ting Xia, Xiaocong Zhou, Funa Cui, Junqi Li, Deqiang Ran, Qingbao Song

Turkish Journal of Chemistry

The Cu(I)-based complex prepared from (S)-2-(furan-2-yl-methylamino)-2-phenylethanol (5c) and CuCl was used as catalyst in enantioselective Henry reactions of arylaldehydes and nitromethane, which gave 89% ee and 95% yield at ambient temperature. The proposed catalytic cycle of an asymmetric Henry reaction was suggested.

Aqueous Red-Emitting Silicon Nanoparticles For Cellular Imaging: Consequences Of Protecting Against Surface Passivation By Hydroxide And Water For Stable Red Emission, Sheng-Kuei Chiu, Beth Ann Manhat, William J.I. Debenedetti, Anna L. Brown, Katye Fichter, Tania Vu, Micah Eastman, Jun Jiao, Andrea Mitchell Goforth

Chemistry Faculty Publications and Presentations

Stable, aqueous, red-to-near infrared emission is critical for the use of silicon nanoparticles (Si NPs) in biological fluorescence assays, but such Si NPs have been difficult to attain. We report a synthesis and surface modification strategy that protects Si NPs and preserves red photoluminescence (PL) in water for more than 6 mo. The Si NPs were synthesized via high temperature reaction, liberated from an oxide matrix, and functionalized via hydrosilylation to yield hydrophobic particles. The hydrophobic Si NPs were phase transferred to water using the surfactant cetyltrimethylammonium bromide (CTAB) with retention of red PL. CTAB apparently serves a double role …

Crystal Structures Of Metal Sulfonates, Jon Lyle Obrecht

Masters Theses

Designing new materials with predictable chemical and physical properties has long been a goal of synthetic chemists. The functional properties of molecular compounds are intimately tied to the underlying chemical framework. In addition to atom selection and chemical connectivity, the spatial organization of the molecules often contributes to the function of materials. Because crystals are constructed of periodic arrays of components (i.e. atoms or molecules) with structures easily assessed via X-ray diffraction, crystalline materials offer ideal candidates to explore the relationship of component selection and crystal packing to material property.

One such property that has been extensively examined by …

From Half-Rotaxanes To Poly-Rotaxane Architectures, Heather Renee Schoonover

Masters Theses

The host-guest abilities of macrocyclic compounds made them important players in the field of supramolecular chemistry, especially those studying mechanical bonds. Rotaxanes and catenanes are among the most well-known examples of mechanically interlocked molecules. Our approach in the synthesis of poly-rotaxane systems involves the preparation of pseudorotaxanes with donor capabilities and then use metallic centers to assemble the poly-rotaxane architectures.

A pyridine-based half-rotaxane has been synthesized and the subsequent solution studies revealed a large association constant. ¹H-NMR studies show that these interlocked species exhibit a slow exchange on the NMR timescale. Using the single point method and VT-NMR several …

The Effect Of Electrochemical Modification On The Surface Topography And Chemical Make-Up Of Strontium Titanate, Kelly J. Harmon

Masters Theses

Previous research into the oxidation and reduction of strontium titanate and the changes that result from this has been carried out. The oxidation and reduction of strontium titanate at high temperatures and high pressures has been investigated for the effect that it has upon the surface topography of strontium titanate and the chemical makeup of the strontium titanate. Research into the electrochemical oxidation of perovskites, similar in structure to that of strontium titanate, have even provided evidence pointing to the identity of the oxygen species being incorporated into the strontium titanate.

This research seeks to investigate what changes occur to …

The Effects Of Chemical Treatment And Light Exposure On Pah Concentrations In Biochar, Fathima Nadheesha Muhammed Khalid

Masters Theses

A series of experiments quantifying extractable polycyclic aromatic hydrocarbons (PAHs) in biochar before and after various treatments were conducted. The analytical approach included solvent extraction of PAHs with toluene, further isolation and column cleanup before gas chromatography mass spectroscopy (GC-MS) analysis. The treatment methods include exposing biochar samples to sunlight and UV radiation with and without additives and reacting with hydrogen peroxide.

Two biochar samples from the Eastern Illinois University bench-type gasifier and commercial biochar were analyzed. Analyzing of three biochar types revealed that plant biochar has lower total PAH concentration than wood (W) biochar or wood and plant (giant …