Open Access Published by De Gruyter Open Access

Volume 4 Issue 4

December 2006

Issue of Open Chemistry

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Journal Overview

Open Access December 1, 2006

Synthesis and characterization of polyaniline-polyvinyl chloride blends doped with sulfamic acid in aqueous tetrahydrofuran

Sadia Ameen, Vazid Ali, M. Zulfequar, M. Mazharul Haq, Mushahid Husain

Page range: 565-577

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Abstract

The temperature dependence of direct current (dc) conductivity was studied for various samples of polyaniline-polyvinylchloride (PANI-PVC) blended films. Polyaniline was doped with different concentrations of sulfamic acid in aqueous tetrahydrofuran (THF) and the blended films were prepared by varying the amount of doped PANI relative to a fixed amount of PVC. The dc conductivity of PANI-PVC blended films was measured to determine the effect of sulfamic acid (dopant) in the temperature range (300–400K). The mechanism of conduction is explained by a two-phase model. In order to evaluate the effect of the dopant, conductivity-derived parameters such as the pre-exponential factor (σ o) and the activation energy (ΔE) were calculated. The structural changes of polyaniline-PVC blended films were characterized by FTIR spectroscopy that explores information about the suitability of the dopant in the chemical doping process.

Open Access December 1, 2006

Conformational studies of aliphatic secondary ozonides (propene, 1-butene and 1-heptene) by means of FTIR spectroscopy

Ruta Bariseviciute, Justinas Ceponkus, Alytis Gruodis, Valdas Sablinskas

Page range: 578-591

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Abstract

Ozonization reaction of simple alkenes was studied by means of FT infrared absorption gas spectroscopy. The reaction was performed at 95 K in neat films of the reactants. IR absorption spectra of the gaseous products were recorded. The spectra were analyzed combining experimental results with theoretical calculations performed at B3LYP 6-311++G (3df, 3pd) level. We found that among all theoretically predicted conformers of propene secondary ozonide, only one which has the O-O half-chair configuration for the five membered ring and the radical attached in the equatorial position was present in the sample. Samples of 1-butene and 1-heptene secondary ozonides consist from two conformers of very similar energy (ΔH=0.3 kJ/mol). The most stable conformer for both ozonides is the one with O-O half-chair configuration of the five membered ring and the radical attached in equatorial position and the aliphatic chain in gauche position. The second stable conformer has the aliphatic chain in anti position.

Open Access December 1, 2006

A new reagent system for the highly sensitive spectrophotometric determination of selenium

Hosakere Revanasiddappa, Banadahalli Dayananda

Page range: 592-603

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Abstract

Highly sensitive and simple spectrophotometric determination of selenium is described for the determination of selenium(IV) using a new reagent leuco malachite green. The method is based on the reaction of selenium(IV) with potassium iodide in an acidic condition to liberate iodine, the liberated iodine oxidizes leuco malachite green to malachite green dye. The green coloration was developed in an acetate buffer (pH 4.2–4.9) on heating in a water bath (∼ 40 °C). The formed dye exhibits an absorption maximum at 615 nm. The method obeys Beer’s law over a concentration range of 0.04–0.4 µg mL−1 selenium. The molar absorptivity and Sandell’s sensitivity of the color system were found to be 1.67 × 105 L mol−1 cm-1 and 0.5 ng cm−2, respectively. The optimum reaction conditions and other analytical parameters have been evaluated. The proposed procedure has been successfully applied to the determination of selenium in real samples of water, soil, plant material, human hair, and cosmetic samples. The results were compared to those obtained with the reference method. Statistical analysis of the results confirms the precision and accuracy of the proposed method. In addition, the developed method is cost-effective and involves easily accessible instrumentation technique which can be used by ordinary research laboratories.

Open Access December 1, 2006

Novel soluble aromatic poly(amideimide)s containing 9,9-diphenylfluorene moieties: characterization and optical properties

Ewa Schab-Balcerzak, Eugenia Grabiec, Bożena Jarząbek, Łukasz Grobelny, Małgorzata Kurcok, Zbigniew Mazurak

Page range: 604-619

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Abstract

A series of aromatic poly(amideimide)s containing 9,9-diphenylfluorene moieties and the amide units in the main chain have been synthesized by solution polycondensation reaction of newly prepared diamidedianhydride with several aromatic diamines: 1,3-phenylenediamine, 3,3′-dimethoxy-biphenyl-4,4′-diamine, 4,4′-oxydianiline, 4,4′-(1,3-phenylenedioxy)dianiline, 4,4′-(9-fluorenylidene)dianiline and 1,5-diaminonaphthalene. Molecular structures of the polymers obtained have been characterized using 13C NMR, 1H NMR and FTIR spectroscopies. The polymers prepared are readily soluble in aprotic polar solvents, and form optically transparent films by solution casting. The resultant poly(amideimide)s have been analyzed by differential scanning calorimetry (DSC), thermogravimetry (TG) and wide-angle X-ray diffraction measurements. They exhibited high levels of thermal stability, with decomposition temperatures in the range 452–494 °C, and high glass transition temperatures (181–278 °C). The optical behavior of these polymers has been investigated in NMP solution as well as in the films. The photoluminescence (PL) spectra of the free-standing films prepared from the poly(amideimide)s exhibited maximum emission bands around 506–525 nm in the green region.

Open Access December 1, 2006

Sequencing peptides by electrospray ion-trap mass spectrometry: A useful tool in synthesis of Axinastatin 3

Chenxi Jia, Wei Qi, Zhimin He, Bin Qiao

Page range: 620-631

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Abstract

Axinastatin 3 as a potential anticancer agent was synthesized by chemical methods. In an electrospray ion-trap mass spectrometer, using one stage of tandem mass spectrometry (MS/MS), the linear peptide intermediate was sequenced via the complementarities of y and b ions. Then, using multistep MS/MS (to MS6), the cyclic peptide was sequenced through sequentially removing one amino acid residue in each stage of MS/MS. The difference of the fragmentation mechanisms and the sequencing approaches between them is discussed.

Open Access December 1, 2006

Synthesis and characterization of Al-and Y-Al-citrates as potential precursors for YAlO3

Nikolina Petrova, Dimitar Todorovsky, Daniela Kovacheva, Maria Milanova

Page range: 632-645

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Abstract

Al-and Y-Al-citric complexes have been synthesized in ethylene glycol medium at conditions close to the ones used in polymerized complex method and their composition and spectral characteristics have been studied. Proofs have been found for the formation in the bimetallic system of a mixed-metal Al-Y-complex. Doubly ionized and esterified ligands take place in the Al-complex. All of the ligands forming Y-Al-complex are mono-or doubly esterified. Deprotonation of the alcoholic group takes place in the formation of the mixed-metal complex. Both complexes contain adduct-bonded ethylene glycol. Heating of the bimetallic complex or of the polyester resin formed leads to not phase-homogeneous YAlO3-along with cubic YAlO3, its orthorhombic modification as well as Y4All2O9 are found by X-ray diffractometry.

Open Access December 1, 2006

Hybrid density functional theory investigation of a series of alloxan-based thiosemicarbazones and semicarbazones

N. Nuwan De Silva, Edward Lisic, Titus Albu

Page range: 646-665

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Abstract

Recently, the synthesis and the NMR characterization of a series of eight alloxan-based thiosemicarbazones and semicarbazones were reported. These compounds exhibit a strongly hydrogenbonded hydrazinic proton that is a part of a characteristic six-membered ring. This proton is highly deshielded and resonates far downfield in the proton NMR spectra. In this report, mPW1PW91/6-31+G(d,p) calculations have been used to investigate the structure and other molecular properties of this series of eight compounds. The relationship between the 1H and 13C NMR chemical shifts and various geometric parameters was investigated, and linear relationships for proton peaks that are involved in hydrogen-bond interactions were found.

Open Access December 1, 2006

Thermal decomposition of ammonia. N2H4-an intermediate reaction product

Daniela Dirtu, Lucia Odochian, Aurel Pui, Ionel Humelnicu

Page range: 666-673

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Abstract

The paper reports the thermal decomposition of ammonia under dynamic conditions at 800°C in a quartz reactor. Its purpose is to confirm the homogeneous-heterogeneous degenerated branched chain mechanism established in previous studies, which assume the formation of N2H4 as a molecular intermediate; this paper identifies hydrazine as a product of thermal decomposition using FT-IR and UV-VIS spectroscopies.

Open Access December 1, 2006

RuO4-mediated oxidation of N-benzylated tertiary amines. 3. Behavior of 1,4-dibenzylpiperazine and its oxygenated derivatives

Horia Petride, Constantin Drăghici, Cristina Florea, Aurica Petride

Page range: 674-694

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Abstract

1,4-Dibenzylpiperazine (1),-2-piperazinone (7),-2,6-piperazinedione (9), and 1-benzoyl-4-benzylpiperazine (30) were oxidized by RuO4 (generated in situ) by attack at their endocyclic and exocyclic (i.e., benzylic) aminic N-α-C-H bonds to afford various oxygenated derivatives, including acyclic diformamides, benzaldehyde, and benzoic acid. The reaction outcome was complicated by (i) the hydrolysis of diformamides, occurred during the work-up, and (ii) the reaction of benzaldehyde with the hydrolysis-derived amines giving imidazolidines and/or Schiff bases. Benzoic acid resulted from benzaldehyde only. Compounds 7, 30, and 1-benzylpiperazine, but not 9, were transiently formed during the oxidation of 1. In the same reaction conditions, 1,4-dibenzyl-2,3-(or 2,5)-piperazinedione, 1,4-dibenzyl-2,3,6-piperazinetrione, 4-benzyol-1-benzyl-2-piperazinone, and 1,4-dibenzoylpiperazine were inert. The proposed oxidation mechanism involves the formation of endocyclic and exocyclic iminium cations, as well as of cyclic enamines. The latter intermediates probably result by base-induced deprotonation of the iminium cations, provided an N +−β-proton is available. In the case of 1, the cations were trapped with NaCN as the corresponding α-aminonitriles. The statistically corrected regioselectivity (endocyclic/exocyclic) of the RuO4-induced oxidation reaction of 1, 7, and 30 was 1.2–1.3.

Open Access December 1, 2006

Solid-state linear-dichroic infrared (IR-LD) spectroscopic and theoretical characterization of 2-[(2-ethoxy-3,4-dioxocyclobut-1-en-yl)amino]propanamide

Sonya Zareva

Page range: 695-707

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Abstract

2-[(2-Ethoxy-3,4-dioxocyclobut-1-en-yl)amino]propanamide (N-alaninamidoamide of squaric acid ethyl ester) has been characterized structurally and spectroscopically by ab initio calculations and IR-LD spectroscopy of oriented crystals suspended in a nematic liquid crystal. The results are compared with single crystal X-ray structures illustrating the possibilities of this experimental approach to obtaining structural information as well as assigning IR bands.

Open Access December 1, 2006

Indirect spectrophotometric determination of gentamicin and vancomycin antibiotics based on their oxidation by potassium permanganate

Akram El-Didamony, Alaa Amin, Ahmed Ghoneim, Ayman Telebany

Page range: 708-722

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Abstract

Four simple, accurate, sensitive and economical procedures (A–D) for the estimation of gentamicin sulphate and vancomycin hydrochloride, both in pure form and in pharmaceutical formulations have been developed. The methods are based on the oxidation of the studied drugs by a known excess of potassium permanganate in sulphuric acid medium and subsequent determination of unreacted oxidant by reacting it with amaranth dye (method A), acid orange II (method B), indigocarmine (method C) and methylene blue (method D), in the same acid medium at a suitable λmax=521, 485, 610 and 664 nm, respectively. The reacted oxidant corresponds to the drug content. Regression analysis of Beer-Lambert plots showed good correlations in the concentration ranges 4–8, 3–8, 4–9 and 5–9 µg ml−1 with gentamicin and 4–8, 1.5–4, 1.5–4 and 3.5–5.5 µg ml−1 with vancomycin for methods A, B, C, and D, respectively. The molar absorptivity, sandell sensitivity, detection and quantification limits were calculated. The stoichiometric ratios for the cited drugs were studied. The optimum reaction conditions and other analytical parameters were evaluated. The influence of the substance commonly employed as excipients with these drugs were studied. The proposed methods were applied to the determination of these drugs in pharmaceutical formulations. The results have demonstrated that the methods are equally accurate and reproducible as the official methods.

Open Access December 1, 2006

Synthesis and electronic properties of pentacene derivatives as promising n-type semiconductor candidates

Chengbin Liu, Yanhong Tang, Shuming Nie

Page range: 723-731

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Abstract

Two pentacene derivatives 1 and 2 were synthesized from the Diels-Alder reactions of furan derivatives with 1,4-benzoquinone. They were characterized by the methods of 1H — nuclear magnetic resonance spectroscopy (1H-NMR), matrix-assisted laser desorption/ionization time of flight mass spectrometry (MALDI-TOF MS), ultraviolet and visible spectrophotometry (UV-VIS), photoluminescence (PL) spectrometry and cyclic voltammetry (CV). The energy gaps of 1 and 2, taken directly from spectroscopic measurements, are broad as 2.72 and 2.46 eV, leading to blue and greenish blue photoluminescence, respectively. The LUMO and HOMO energy levels are −2.77 and −5.49 eV for 1, and −2.91 and −5.37 eV for 2, respectively. The low energy levels make both 1 and 2 good air-stabilities and promising n-type semiconductor candidates for use in organic electronics.

Open Access December 1, 2006

Hydrogen-bonded assembly and binding affinity of the multi-point acceptor and isophthalic acid

Lingjia Xu, Liangliang Zhu, Shi Wu, Xiaopeng Chen, Qiwen Teng

Page range: 732-742

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Abstract

Supermolecular complexes formed by oligophenyleneethynylene derivatives and isophthalic acid were studied using AM1 method to obtain binding energy. Electronic spectra and IR spectra of the complexes were calculated by INDO/CIS and AM1 methods based on AM1 geometries. Results indicated that the dimer could be formed by the monomers via hydrogen bonding because of the negative binding energy. Binding energy of the complexes was affected by electronegativity and steric effects of the substituents. The first UV absorptions and IR frequencies of N-H bonds of the complexes were both red-shifted compared with those of the monomers. The complexes could bind small molecules via hydrogen bonds, resulting in the change in UV absorptions and an increase in IR frequencies of N-H bonds.

Open Access December 1, 2006

Enhancement of molecular polarizabilities by the push-pull mechanism; a DFT study of substituted benzene, furan, thiophene and related molecules

Alan Hinchliffe, Ahmed Mkadmh, Beatrice Nikolaidi, Humberto Soscún, Fakhr Abu-Awwad

Page range: 743-759

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Abstract

We report Density Functional Theory (DFT) studies of the dipole polarizabilities of benzene, furan and thiophene together with a number of substituted and related systems. All geometries were optimized (and characterized) at the B3LYP/6-311g(2d,1p) level of theory and polarizabilities then calculated with B3LYP/6-311++G(2d,1p). For the R-ring systems we find group polarizabilities in the order R = NO2 ∼ OCH3 ∼ CN ∼ CHO > NH2 > OH > H = 0. For systems R-ring-R, 〈α〉 differs little from the additivity model, with small positive and negative increments. For systems D-ring-A (where D and A are deactivating and activating groups) we find a positive enhancement to 〈α〉 over and above the value expected on the basis of pure additivity for all pairs A and D studied. This enhancement can be increased greatly by extending the length of the conjugated chain to D-ring-CH=CH-ring-A and D-ring-N=N-ring-A systems. Empirical models of polarizability such as AM1 agree badly with the DFT calculations in an absolute sense but give excellent statistical correlation coefficients. Calculated 〈α〉’s also agree well in a statistical sense with the molecular volumes calculated from molecular mechanics force fields Analysis of the results in terms of the π electrons alone is not satisfactory.

Open Access December 1, 2006

X-ray powder diffraction study of chromium-vanadium oxide compounds prepared by “soft chemistry” methods

O. Pozdnyakova, J. Megyeri, E. Kuzmann, L. Szirtes

Page range: 760-772

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Abstract

A novel aqueous method was used to synthesise mixed chromium-vanadium oxide hydrates with various chromium content, via the reaction of peroxo-polyacids of chromium and vanadium. The resulting materials are gelatinous. The dehydration of the gels result in a brown coloured amorphous powder. Depending on the chromium content, the compounds have a different characteristic crystallisation temperature upon the further heating. The crystalline compounds, except for the low chromium ones, go on a phase transition and decompose with increasing temperature. By refining the XRPD measurement data of the compounds, the type and parameters of the unit cells were determined. The experimental data were in concordance with the calculated values, using the PWC code. The lattice parameters and the crystalline structure were changed with the variation of chromium content.

Open Access December 1, 2006

Scaled quantum chemical studies of the structural and vibrational spectra of acetyl coumarin

Khaled Bahgat

Page range: 773-785

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Abstract

The solid phase FT-IR and FR-Raman spectra of acetyl coumarin have been recorded in the regions 4000–50 cm−1. The spectra were interpreted with the aid of normal coordinate analysis following full structure optimization and force field calculations based on density functional theory (DFT) and Hartree-Fock (HF) at 6–31G* and 6–311++G** basis sets. The resulting force fields were transformed to internal coordinates, the calculated vibrational frequencies and normal modes were utilized in the assignment of the observed vibrational fundamentals. The measured spectral data were used to refine the vibrational force constants by means of a small number of scaling factors.

Open Access December 1, 2006

Spectroscopic methods of studying enzyme action in wool fibre

Magdalena Fogorasi, Elisabeth Heine

Page range: 786-797

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Abstract

Enzymes may be used to develop an environmentally friendly alternative to the conventional polluting technologies in textile finishing. The action of the unlabeled and fluorescent labeled proteolytic enzymes subtilisin and trypsin on wool was examined. Scanning electron micrographs and a diffusion study, based on fluorescence microscopy, localized the enzymatic attack on the fiber. A kinetic study was carried out by monitoring the amino acid content of the treatment liquor. Enzymatic action is not confined to the fiber surface. To limit attack to the surface and reduce wool damage new treatment methods such as enzyme immobilization onto a solid carrier must be investigated.

Open Access December 1, 2006

Simultaneous determination of fluoride and monofluorophosphate in toothpastes by supressed ion chromatography

Rajmund Michalski, Barbara Mathews

Page range: 798-807

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Abstract

Suppressed ion chromatography with a highly selective and high capacity anion-exchange column is used for the determination of anionic compounds in ten commercially available toothpastes. Minimal sample preparation is needed, requiring only dilution and filtration over a solid-phase extraction cartridge. Quantitative analysis of fluoride and monofluorophosphate, as well as chloride, nitrate, orthophosphate, and sulfate is achieved in one chromatographic run with a total analysis time of 25 minutes. Optimized analytical conditions are validated in terms of accuracy, precision, and total uncertainty, and the results demonstrate the reproducibility of ion chromatography. The coefficient of determination for the anions ranges from 0.9896 to 0.9997. The spiked recoveries for the anions are 88–108%. The change in the fluoride content of the toothpaste with storage time is investigated.

Open Access December 1, 2006

Synthesis and stereochemistry of some new 1,3,5-tris(1,3-dioxan-2-yl)-benzene derivatives

Maria Florian, Monica Cîrcu, Loïc Toupet, Anamaria Terec, Ion Grosu, Yvan Ramondenc, Nicolae Dincă, Gerard Plé

Page range: 808-821

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Abstract

The synthesis and the stereochemistry of new 1,3,5-tris(1,3-dioxan-2-yl)-benzene derivatives are reported. The anancomeric structure and the axial orientation of the aryl group with respect to all 1,3-dioxane rings, and the cis-trans isomerism of some of the compounds are revealed. The data are supported by NMR investigations and by the molecular structure of one compound determined by single crystal X-ray diffractometry.

Open Access December 1, 2006

DECSERVIS: a tool for radioactive decay series visualisation

Saad Azzam, Juhani Suksi

Page range: 822-834

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Abstract

We have developed an interactive visualisation tool, decay series visualisation (DECSERVIS), for exploring the three natural radioactive decay chains. Through DECSERVIS, one can investigate the full decay scheme of any natural decay chain radionuclide to obtain the number of nuclides, their masses, activities, and activity ratios, accounting for all the daughters, starting from initial conditions freely chosen by the user. The tool has been developed particularly for user friendly and flexible operation. Chain decay in closed systems can be explored as a function of time with various graphical presentations such as solid curve and column diagrams or animation. We present several exploration examples related to geological dating. DECSERVIS will be freely available on request.

About this journal

Open Chemistry is a peer-reviewed, open access journal that publishes original research, reviews, and communications in the fields of chemistry in an ongoing way. Our central goal is to provide a hub for researchers working across all subjects to present their discoveries, and to be a forum for the discussion of the important issues in the field.

There are no submission charges. In order to sustain the production of our fully-refereed open access journal, each article accepted for publication in Open Chemistry is subject to Article Processing Charges (APC).

Special/Topical Issues:

Advanced Nanomaterials for Energy, Environmental and Biological Applications
Submission deadline: 30.09.2023
Marine Environmental Sciences and significance of the multidiscplinary approaches for assessing pollutions, remedies, and predictions
Submission deadline: 30.09.2023
Energy conversion and energy storage reactions
Submission deadline: 30.09.2023
Recent Trends in Green Chemistry
Submission deadline: 30.09.2023
Therapeutic Potentials of Natural Compounds Targeting Malaria
Submission deadline: 30.09.2023
Advancements at the Nexus of Mathematics, Artificial Intelligence, and IoT in Medicinal Chemistry and Healthcare
Submission deadline: 30 June 2024

You are also welcome to submit your Special Issue proposal by contacting Managing Editor at openchemistry@degruyter.com

Cooperation with conferences:

Catalysis Conferences
Submission deadline: 30.09.2023
MATERIALS and MAT Conferences 2023
Submission deadline: 30.09.2023
Euro-Mediterranean Conference for Environmental Integration 2023
Submission deadline: 30.10.2023
CFP Applied Biochemistry and Biotechnology 2023
Submission deadline: 30.11.2023
World Chemistry Forum 2024
Date: 1.02 - 3.02.2024
2nd International Summit on Biopolymers and Polymer Science
Date: 10-12.06.2024
4th Edition of the International Conference on Green Chemistry and Renewable Energy
Date: 17-19.06.2024
11th International Conference on Materials Research and Nanotechnology
Date: 1.07 – 2.07.2024
2nd Global Summit on Advanced Materials and Sustainable Energy (GAMSE24)
Submission Deadline: 31.07.2024
European Congress of Applied Chemistry (ECAC24)
Submission Deadline: 31.07.2024