Dodecanoyl isothiocyanate and N′-(2-cyanoacetyl) dodecanehydrazide as precursors for the synthesis of different heterocyclic compounds with interesting antioxidant and antitumor activity

Dodecanoyl isothiocyanate 1 was utilized for the construction of thioureido, 2-thioxo-2,3-dihydroquinazolin-4(1H)-one, benzo[d]-1,3-thiazin-4(H)-one and 3-amino quinazolin-4(3H)-one derivatives 2, 3, 4, and 5 respectively. However, N′-(2-cyanoacetyl) dodecanehydrazide 6 was also used as a key starting material for the construction of a variety of new pyrazolone, pyrazole, thiadiazole, pyridazine, chromeno[2,3-c]pyrazole, and dithiolane derivatives 7, 9, 12, 15, 18, and 20, respectively. The newly synthesized compounds were characterized by elemental analyses and spectral data (IR, ¹H NMR, and mass spectra). Some of the newly synthesized compounds bearing heterocyclic moieties were tested for antioxidant activity as reflected in their ability to inhibit oxidation in rat brain and kidney homogenates using 2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) inhibition. Also, in vitro anticancer activity was examined using the standard (3-(4,5-dimethylthiazolyl-2)-2,5-diphenyltetrazolium bromide) (MTT) method against a panel of two human tumor cell lines namely; hepatocellular carcinoma HepG2 and mammary gland breast cancer MCF-7. Compounds 12 and 16b exhibited the highest activities as antioxidant and antitumor agents. Meanwhile, compounds 7 and 20 showed moderate activities and the rest of the tested compounds showed weak activities.     

A glassy carbon electrode with electrodeposited silver nanoparticles for aptamer based voltammetric determination of trinitrotoluene using riboflavin as a redox probe

An electrochemical nanoaptasensor is described that is based on the use of a glassy carbon electrode (GCE) modified with electrodeposited silver nanoparticles (AgNPs). An aptamer (Apt) against trinitrotoluene (TNT) was then immobilized on the AgNPs. The addition of TNT to the modified GCE leads to decrease in peak current (typically measured at a potential of ?0.45 V vs. Ag/AgCl) of riboflavin which acts as an electrochemical probe. Even small changes in the surface (as induced by binding of Apt to TNT) alter the interfacial properties. As a result, the LOD is lowered to 33 aM, and the dynamic range extends from 0.1 fM to 10 μM without sacrificing specificity.

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Graphical abstract Schematic presentation of a nanoaptasensor which is based on a glassy carbon electrode (GCE) modified with electrodeposited silver nanoparticles (AgNPs) and aptamer (Apt). It was applied to the detection of 2,4,6-trinitrotoluene (TNT) with the help of riboflavin (RF) as a redox probe.

     

Alkali halides based on nano-alumina as positive and negative ion source for ion mobility and mass spectrometry

In this work, a new long-life alkali ion source is proposed that is based on alkali halide salts doped in nano-γ-alumina (Al₂O₃). Depending on the polarity, the ion source produces both alkali and halide ions. The source was characterized using different techniques such as scanning electron microscopy (SEM), transmission electron microscope (TEM), X-ray diffraction (XRD), fourier transform infrared (FT-IR), and ion mobility spectrometry (IMS). SEM images confirm a strong interaction between the alkali halide (MX) and nano-γ-alumina. The average particle size of the doped nanoparticles was calculated to be 44 nm by TEM. Formation of new phases (KAlCl₂O and K₃AlF₆) was confirmed by XRD and that of Al–O–K group in the synthesized particles by FT-IR. Alkali and halide ion peaks were observed by IMS in the positive and negative modes, respectively. The lifetime of the ion source for different alkali halides was measured to range from 216 to 960 h. The total ion current emitted from the source was about 2 µA, while it was 12 nA at the collector plate of the IMS. Finally, application of the new source in ion mobility spectrometry was demonstrated by observing ion mobility spectra of compounds ionized via cation and anion attachment reaction.     

Electrochemical sensing and simultaneous determination of ascorbic acid,dopamine and uric acid at nickel nanoparticles/poly (1,2-diaminoanthraquinone) modified electrode

A highly sensitive sensor based on Ni nanoparticles/poly (1,2-diaminoanthraquinone) modified electrode was fabricated at glassy carbon (GC) electrode (Ni/PDAAQ@GC ME) using cyclic voltammetry technique. The incorporation of nickel (II) ions nanoparticles (Ni NPs) followed by anodic polarization process was achieved. Surface morphologies of both PDAAQ@GC ME and Ni/PDAAQ@GC MEs were studied by scanning electron microscope. Ni/PDAAQ@GC ME was tested for simultaneous determination of ascorbic acid (AA), dopamine (DA) and uric acid (UA) by square wave voltammetry technique. The ME showed excellent electrocatalytic activity toward electrooxidation of these biomolecules in their single, binary and ternary systems in alkaline 0.1 M NaOH solutions. Experiment revealed that the low detection limits (LOD) for AA, DA and UA were 0.11, 0.072 and 1.2 µM in single system, respectively, and 0.069, 0.29 and 0.12 µM in ternary system, respectively.     

HPLC and chemometrics-assisted UV-spectroscopy methods for the simultaneous determination of ambroxol and doxycycline in capsule

High-performance liquid chromatography (HPLC) and multivariate spectrophotometric methods are described for the simultaneous determination of ambroxol hydrochloride (AM) and doxycycline (DX) in combined pharmaceutical capsules. The chromatographic separation was achieved on reversed-phase C(18) analytical column with a mobile phase consisting of a mixture of 20mM potassium dihydrogen phosphate, pH 6-acetonitrile in ratio of (1:1, v/v) and UV detection at 245 nm. Also, the resolution has been accomplished by using numerical spectrophotometric methods as classical least squares (CLS), principal component regression (PCR) and partial least squares (PLS-1) applied to the UV spectra of the mixture and graphical spectrophotometric method as first derivative of the ratio spectra ((1)DD) method. Analytical figures of merit (FOM), such as sensitivity, selectivity, analytical sensitivity, limit of quantitation and limit of detection were determined for CLS, PLS-1 and PCR methods. The proposed methods were validated and successfully applied for the analysis of pharmaceutical formulation and laboratory-prepared mixtures containing the two component combination.     

Validated spectrofluorometric methods for determination of amlodipine besylate in tablets

Two simple and sensitive spectrofluorometric methods have been developed and validated for determination of amlodipine besylate (AML) in tablets. The first method was based on the condensation reaction of AML with ninhydrin and phenylacetaldehyde in buffered medium (pH 7.0) resulting in formation of a green fluorescent product, which exhibits excitation and emission maxima at 375 and 480 nm, respectively. The second method was based on the reaction of AML with 7-chloro-4-nitro-2,1,3-benzoxadiazole (NBD-Cl) in a buffered medium (pH 8.6) resulting in formation of a highly fluorescent product, which was measured fluorometrically at 535 nm (lambda(ex), 480 nm). The factors affecting the reactions were studied and optimized. Under the optimum reaction conditions, linear relationships with good correlation coefficients (0.9949-0.9997) were found between the fluorescence intensity and the concentrations of AML in the concentration range of 0.35-1.8 and 0.55-3.0 microg ml(-1) for ninhydrin and NBD-Cl methods, respectively. The limits of assays detection were 0.09 and 0.16 microg ml(-1) for the first and second method, respectively. The precisions of the methods were satisfactory; the relative standard deviations were ranged from 1.69 to 1.98%. The proposed methods were successfully applied to the analysis of AML in pure and pharmaceutical dosage forms with good accuracy; the recovery percentages ranged from 100.4-100.8+/-1.70-2.32%. The results were compared favorably with those of the reported method.     

Vibrational analysis of amino acids and short peptides in hydrated media. 3. Successive KL repeats induce highly stable beta-strands capable of forming non-H-bonded aggregates

Circular dichroism (CD) and Raman scattering were applied to the aqueous solution of minimalist LK peptides constructed with successive KL repeats leading to the following generic primary sequence: (KL)nK. Three peptides of this family, a 3-mer (n=1), a 9-mer (n=4), and a 15-mer (n=7), are analyzed in this report. Raman spectra of the 3-mer (KLK, a random chain) and its labile-hydrogen deuterated species yield a set of interesting information for analyzing longer peptides of this series. Although the CD spectrum of the 9-mer (KLKLKLKLK) reveals a signal traditionally assigned to a random structure, the corresponding Raman spectrum allows finding a mixture of conformations in solution, adopting predominantly beta-type structures. This fact proves the utility of Raman spectroscopy to eliminate eventual ambiguity concerning conformational assignments in peptides based only on the use of CD technique. Finally, the 15-mer (KLKLKLKLKLKLKLK) gives rise to CD and Raman spectra clearly assignable to a beta-type structure. On the basis of all the observed results on the 15-mer, we can confirm that this peptide may exist as isolated beta-strands at low concentration (sub-micromolar), flat-oriented at the air/water interface, whereas at high concentrations (millimolar), non-H-bonded immersible aggregates might be formed. A hypothetical model for these beta-strand aggregates could be proposed as stabilized by an interior hydrophobic core and a hydrophilic external face, formed by leucine and lysine side chains, respectively.     

C-Furyl glycosides, I: Synthesis and antimicrobial evaluation of C-furyl glycosides and chalcones derived therefrom

New C-furyl glycosides were synthesized in order to increase the number of compounds screened for antimicrobial activity. The antimicrobial activity showed that the bromo as well as the nitro derivatives were the most active compounds. Correspondence: Adel A.-H. Abdel-Rahman, Faculty of Science, Department of Chemistry, Menoufia University, Shebin El-Koam, Egypt.