Feasibility of radiation sterilization and dosimetric features of ampicillin: an electron spin resonance study

In the present work, it was aimed to identify radical species produced by gamma irradiation (3–34?kGy) of solid ampicillin, to determine its spectroscopic, dosimetric, stability and kinetic behavior, and to investigate feasibility of the radiation sterilization feature of ampicillin by using electron spin resonance (ESR) spectroscopy. ESR experiments were performed at low and high temperatures (130–400?K) to examine the characteristic properties of the radical intermediates that are produced in ampicillin by gamma radiation treatment. Unirradiated ampicillin presented no ESR signal but irradiated samples exhibited ESR spectra with four resonance peaks spread over a magnetic field range of 8?mT. The spectral parameters of the central resonance line of the spectrum are g?=?2.0044 and ΔH_pp?=?0.08?mT. An exponential growth function of the applied dose was found to describe best the experimental dose–response data and it was found that ampicillin did not exhibit the feature of a good dosimetric material as its ESR intensity was relatively weak even for the samples irradiated at high level of doses. G_mean value of gamma-irradiated ampicillin was found to be 4.6?±?0.9?×?10^?9?mol/J, which is very small compared to irradiated alanine solid sample. However, the discrimination of irradiated ampicillin from unirradiated one was possible even ～3 months after storage at normal conditions. The simulation calculations indicated that gamma irradiation created two different radical species in solid ampicillin. Decay activation energy of the radical species which is mostly responsible from central intense resonance line is calculated to be 55.6?±?3.2?kJ/mol by using the signal intensity decay data derived from annealing studies. It was concluded that ampicillin could be sterilized by gamma radiation and ESR spectroscopy can be used as a potential technique to monitor its radiosterilization process.     

Synthesis, spectral and thermal properties, and crystal structure of catena-poly-μ-ethylenediamine(dipicolinato)zinc(II) trihydrate, {[Zn(dipic)(μ-en)]·3H2O}n

A novel metal–organic coordination polymer framework formulated as {[Zn(dipic)(μ-en)]·3H₂O} _n (1) (catena-poly-μ-ethylenediamine(dipicolinato)zinc(II) trihydrate) has been synthesized and characterized by spectral method (IR), elemental analysis, thermal analysis (TG, DTG, DTA) and single crystal X-ray diffraction techniques. It crystallizes in the triclinic system, space group P−1. The asymmetric unit contains three hydrogen-bonded water molecules and the Zn atom is five-coordinated by three N and two O atoms. In fact, it is a new one-dimensional zinc complex with the peculiarity of having the ethylenediamine ligand very unusually acting as bridge to form polymeric chains. In the crystal structure, intramolecular O–H···O and intermolecular O–H···O and N–H···O hydrogen bonds result in the formation of a supramolecular structure, in which they seem to be effective in the stabilization of the structure.     

Modeling and predicting binding affinity of phencyclidine‐like compounds using machine learning methods

Machine learning methods have always been promising in the science and engineering fields, and the use of these methods in chemistry and drug design has advanced especially since the 1990s. In this study, molecular electrostatic potential (MEP) surfaces of phencyclidine‐like (PCP‐like) compounds are modeled and visualized in order to extract features that are useful in predicting binding affinities. In modeling, the Cartesian coordinates of MEP surface points are mapped onto a spherical self‐organizing map (SSOM). The resulting maps are visualized using electrostatic potential (ESP) values. These values also provide features for a prediction system. Support vector machines and partial least‐squares method are used for predicting binding affinities of compounds. Copyright © 2009 John Wiley & Sons, Ltd.     

Synthesis, spectroscopic, thermal, crystal characterization and biological activity of [Ni(phen)3][Ni(dipic)2]2.17H2O (H2dipic:pyridine-2,6-dicarboxylic acid, phen: 1,10-phenanthroline)

The new [Ni(phen)₃][Ni(dipic)₂]₂.17H₂O (1) (phen = 1,10-phenanthroline, dipic = dipicolinate)) has been prepared and characterized by elemental analysis, IR, UV-Vis, magnetic measurement and single crystal X-ray diffraction. The complex consists of two tris(1,10-phenanthroline)nickel(II) cations, two bis(dipicolinato)nickelate(II) anions and seventeen uncoordinated water molecules. The Ni(II) complex crystallizes in the triclinic space group P-1. The complex consisting of cation has distorted octahedral coordination by three bidentate phen ligands. In the complex anion, each dipic ligand simultaneously exhibits tridentate coordination modes through N atom of pyridine ring and oxygen atoms of the carboxylate groups. The crystal packing of 1 is a composite of intermolecular hydrogen bonding, π-π and C-H?π interactions. The complex has also been investigated in terms of biological activity and it showed high activity against S. aureus from Gram positive bacteria and C. albicans from yeast tested.     

Sampling hazelnuts for aflatoxin: uncertainty associated with sampling, sample preparation, and analysis

The variability associated with the aflatoxin test procedure used to estimate aflatoxin levels in bulk shipments of hazelnuts was investigated. Sixteen 10 kg samples of shelled hazelnuts were taken from each of 20 lots that were suspected of aflatoxin contamination. The total variance associated with testing shelled hazelnuts was estimated and partitioned into sampling, sample preparation, and analytical variance components. Each variance component increased as aflatoxin concentration (either B1 or total) increased. With the use of regression analysis, mathematical expressions were developed to model the relationship between aflatoxin concentration and the total, sampling, sample preparation, and analytical variances. The expressions for these relationships were used to estimate the variance for any sample size, subsample size, and number of analyses for a specific aflatoxin concentration. The sampling, sample preparation, and analytical variances associated with estimating aflatoxin in a hazelnut lot at a total aflatoxin level of 10 ng/g and using a 10 kg sample, a 50 g subsample, dry comminution with a Robot Coupe mill, and a high-performance liquid chromatographic analytical method are 174.40, 0.74, and 0.27, respectively. The sampling, sample preparation, and analytical steps of the aflatoxin test procedure accounted for 99.4, 0.4, and 0.2% of the total variability, respectively.     

Compressed images for affinity prediction (CIFAP): a study on predicting binding affinities for checkpoint kinase 1 protein inhibitors

Analyses of known protein–ligand interactions play an important role in designing novel and efficient drugs, contributing to drug discovery and development. Recently, machine learning methods have proven useful in the design of novel drugs, which utilize intelligent techniques to predict the outcome of unknown protein–ligand interactions by learning from the physical and geometrical properties of known protein–ligand interactions. The aim of this study is to work through a specific example of a novel computational method, namely compressed images for affinity prediction (CIFAP), in which binding affinities for structurally related ligands in complexes with human checkpoint kinase 1 (CHK1) are predicted. The CIFAP algorithm presented here relates published pIC ₅₀ values of 57 compounds, derived from a thienopyridine pharmacophore, in complexes with CHK1 to their two‐dimensional (2D) electrostatic potential images compressed in orthogonal dimensions. Patterns obtained from the 2D images are then used as inputs in regression and learning algorithms such as support vector regression (SVR) and adaptive neuro‐fuzzy inference system (ANFIS) methods to validate the experimental pIC ₅₀ values. This study revealed that the 2D image pixels in the vicinity of bound ligand surfaces provide more relevant information to make correlations with the empirical pIC ₅₀ values. As compared with ANFIS, SVR gave rise to the lowest root mean square errors and the greatest correlations, suggesting that SVR could be a plausible choice of machine learning methods in predicting binding affinities by CIFAP. Copyright © 2013 John Wiley & Sons, Ltd.     

Monitoring Humic Acid Photodegradation by CUPRAC Colorimetric and HPLC Determination of Dihydroxybenzoate Isomers Produced From a Salicylate Probe

Abstract

Novel analytical methods were designed for monitoring humic acid photodegradation in environmental waters. Modified CUPric Reducing Antioxidant Capacity (CUPRAC) spectrophotometric and chromatographic methods were used for the determination of dihydroxybenzoate isomers (DHBAs) produced from a salicylate probe, which was hydroxylated by hydroxyl radicals (^?OH) produced from the photodegradation of humic acid under ultraviolet A-radiation. The combined use of CUPRAC colorimetry and HPLC was shown to effectively monitor humic acid photodegradation and ^?OH generation for the first time. The formation of 2,5-dihydroxybenzoate and 2,3-dihydroxybenzoate, as major and minor products, respectively, from the hydroxylation of a salicylate probe was demonstrated by HPLC and confirmed by a modified CUPRAC method to indicate ^?OH formation from humic acid, which acted as both a generator and absorber of hydroxyl radicals. Salicylate hydroxylation showed an increase between 30 and 50?min of illumination, and was affected by the initial concentration of humic acid up to 0.01% but not by solution pH around the neutral values. Traces of Fe(III) and Mn(II) present in natural waters decreased the ^?OH production, but EDTA partly restored the probe hydroxylation by chelating these metal cations. Since humic acid-mediated ^?OH generation may aid in natural disinfection processes, this work may extend our comprehension of concentration- and time-dependent generation of ^?OH in environmental waters and of the possible effects of other antioxidants.     

Synthesis,Spectroscopic Studies and Crystal Structure of <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>′-bis((thiophene-2-carboxamido)propyl)piperazine

Abstract  A new multidentate ligand N,N′-bis((thiophene-2-carboxamide)propyl)piperazine has been synthesized from the reaction of thiophene-2-carbonylchloride and 1,4-bis(3-aminopropyl)piperazine. The title compound has been characterized by elemental analysis, FT-IR, ¹H-NMR and ¹³C-NMR spectroscopic techniques. The crystal structure of the title compound (C₂₀H₃₀N₄O₂S₂Cl₂) has also been determined by X-ray analysis. The title compound crystallize in the monoclinic space group P2₁/c with a = 9.768(1), b = 12.895(1), c = 10.083(1) ?, β = 115.12(1)°, V = 1149.9(2) ?³, D _x = 1.425 g cm⁻³ and Z = 2. The crystal structure was solved by direct methods and refined by full-matrix least squares to a find R = 0.039 [I > 2σ (I)] for 2,786 observed reflections. Graphical Abstract  The (N,N’–bis((thiophene-2- carboxamido)propyl)piperazine) molecule has been synthesized and its molecule structure has been investigated by using , FT-IR, 13C NMR and 1H-NMR spectroscopic and crystallographic techniques.

Synthesis,structural characterization and biological activities of metal(II) complexes with Schiff bases derived from 5-bromosalicylaldehyde: Ru(II) complexes transfer hydrogenation

In this study, two novel Schiff base ligands (L¹ and L²) derived from condensation of methyl 2-amino-6-methyl-4,5,6,7-tetrahydrothieno[2,3-c]pyridine-3-carboxylate and methyl 2-amino-6-phenyl-4,5,6,7-tetrahydrobenzo[b]thiophene-3-carboxylate, both starting matter with 5-bromo-salicylaldehyde, and their Zn(II) and Ni(II) metal complexes have been prepared using a molar ratio of ligand:metal as 1:1 except the Ru(II) complexes 1:0.5. The structures of the obtained ligands and their metal complexes were characterized by elemental analysis, FT-IR, ¹H NMR, ¹³C NMR, UV–vis, thermal analysis methods, mass spectrometry, and magnetic susceptibility measurements. Antioxidant and antiradical activity of Schiff base ligands and their metal complexes were been evaluated in vitro tests. Antioxidant activities of metal complexes generally were more effectives than free Schiff bases. 1c and 2c were used as catalysts for the transfer hydrogenation (TH) of ketones. 1c, 2c complexes were found to be efficient catalyst for transfer hydrogenation reactions.     

Synthesis,crystal structures,characterization and antimicrobial activities of 5-hydroxyisophthalate complexes

Two 5-hydroxyisophthalate complexes of nickel(II), formulated as [Ni(μ-Hhip)(2-hepy)₂] _n (1) and [Ni₂(μ-Hhip)₂(dap)₄] _n (2) (H₃hip = 5-hydroxyisophthalic acid, 2-hepy = 2-(2-hydroxyethyl)pyridine, dap = 1,3-diaminopropane), have been synthesized and characterized by chemical and spectroscopic methods. The molecular structures of the complexes have been determined by single-crystal X-ray diffraction analysis. The Ni(II) centres have distorted octahedral geometries in both crystals. Furthermore, both complexes have 1D chain structures in which the individual chains are linked together via hydrogen bonds to give 3D frameworks. Evaluation of the complexes by the agar diffusion method showed that they have weak antibiotic activities against the tested microorganisms.