Open Access Published by De Gruyter Open Access

Volume 12 Issue 1

January 2014

Issue of Open Chemistry

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Journal Overview

Open Access October 27, 2013

Current uses and trends in catalytic isomerization, alkylation and etherification processes to improve gasoline quality

José Hidalgo, Michal Zbuzek, Radek Černý, Petr Jíša

Page range: 1-13

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Abstract

Due to the growing restrictions on the content of aromatic compounds by the European legislation in motor fuels and at the same time the need for higher quality fuels (minimizing the presence of contaminants and hazardous products to health), it has become necessary to increase processes that can maximize the number of octane in gasoline. This manuscript is aimed to provide current trends and processes related to isomerization, alkylation and etherification processes to improve gasolines as final product. Examples provided include the isomerization of light n-alkanes into iso-alkanes or the alkylation, in which the preferred olefin is the methylbutilene and i-butane to produce a high octane number gasoline. Currently, there are two main commercial processes for alkylation processes (hydrofluoric and sulfuric acid technologies). Other incoming suitable process is the etherification of iso-olefins to bio-ethers (the European Union have as a minimum target of biofuel content in fuels of 10% in 2020). The refiners are recently investing in the production of bio-ETBE (ethyl tertiary butyl ether) and other products as additives using bio-ethanol and olefins. Commercial and new potential catalysts for all these processes are currently being used and under investigation.

Open Access October 27, 2013

Hydrogen bonding-based 3D supramolecular architecture of [Cu(CHA)2][TCM]·11H2O

Mihaela Vlassa, Gheorghe Borodi, Cristian Silvestru, Mircea Vlassa

Page range: 14-24

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Abstract

Reaction of Na4TCM (1) (H4TCM = tetra[4-(carboxyphenyl)oxamethyl]methane) with [Cu(CHA)](ClO4)2 (2)(CHA = 1,3,6,8,11,14-hexaaz atricyclo[12.2.1.1.8,11] octadecane) in a DMF-water mixture yields [Cu(CHA)]2[TCM] (3). Structural analysis of [Cu(CHA)]2[TCM]·11H2O (3·11H2O) by single crystal X-ray diffraction reveals strong copper-oxygen bonds between two complex cations and the tetraanion leading to a 3D coordination network (zwitterionic structure), consolidated through additional NH...O=C hydrogen bonding within the cation/anion association. The resulting coordination geometry around a copper atom is a distorted square pyramidal with an oxygen atom of the anionic ligand in the apical position. A 3D supramolecular network is developed in the crystal based only on NH...OC hydrogen bonds between the macrocyclic metallic tecton and the carboxylate groups of neighboring 3D coordinated (zwitterionic) moieties. The pseudotetrahedral TCM4− tetraanionic ligand induces a diamondoid architecture formed of large distorted adamantanoid cages.

Open Access October 27, 2013

Enzyme-catalyzed kinetic resolution of N-Boc-trans-3-hydroxy-4-phenylpyrrolidine

Ferenc Faigl, Ervin Kovács, Dóra Balogh, Tamás Holczbauer, Mátyás Czugler, Béla Simándi

Page range: 25-32

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Abstract

The first enzyme-catalyzed kinetic resolution of tert-butyl-3-hydroxy-4-phenylpyrrolidine-1-carboxylate is presented. Enzyme, solvent and temperature optimization resulted in a new resolution method with E = 40 enantioselectivity. The acetate derivative of the (+)-(3S,4R) enantiomer formed while the (−)-(3R,4S) isomer remained intact. Very good enantioselectivities (E > 200) were achieved in the enzyme-catalyzed alcoholysis of the racemic acetate in i-propanol and t-butanol where the (+)-(3S,4R) enantiomer was prepared in pure form (ee > 99.7%). Absolute configuration of the (−)-(3R,4S)-enantiomer was determined by single crystal X-ray diffraction method.

Open Access October 27, 2013

Cation exchange capability and reactivity of low-rank coal and chars

George Skodras, Paris Kokorotsikos, Maria Serafidou

Page range: 33-43

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Abstract

In this work the C.E.C. and its effect on the reactivity of low rank coal and chars were investigated. The C.E.C. was measured by potentiometric titration and was correlated with the solution pH, the carbonization extent and the oxygen content. Coal and chars presented permanent C.E.C. primarily derived from inorganic sites and was independent of solution pH, and variable C.E.C. derived from organic matter and was increased continuously, and reversibly, as the solution pH increased. The latter is due to the complete dissociation of the carboxylic groups of the organic matter of the coal and, thus, the C.E.C. is directly related with the oxygen content. The C.E.C. of chars decreased with the carbonization extents and its variation was described by a modified cumulative distribution function of the Weibull probability density function. A linear correlation was identified between the C.E.C. and the elemental oxygen conversion, justifying further the direct relation between the C.E.C. and the oxygen functional groups. Following the decrease of the C.E.C., the potassium chemisorption capacity of the chars also decreased. Chars of decreased C.E.C. were less reactive during CO2 gasification and reduced maximum weight loss and CO formation rates were obtained, also shifted at higher temperatures.

Open Access October 27, 2013

Microspectroscopic infrared specular reflection chemical imaging of multi-component urinary stones: MIR vs. FIR

Milda Pucetaite, Sandra Tamosaityte, Anders Engdahl, Justinas Ceponkus, Valdas Sablinskas, Per Uvdal

Page range: 44-52

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Abstract

Specular reflection infrared microspectroscopy was used for chemical imaging of cross-sectioned urinary stones to determine their chemical composition and morphology simultaneously. Absorption spectral bands were recovered from reflection spectra by Kramers-Kronig transform. FUse of far-infrared radiation provides high-contrast images and allows more precise constituent distribution determinations than mid-infrared because band asymmetry after the transform caused by diffuse reflection is less in the far-infrared.

Open Access October 27, 2013

Influence of point defects on the structural and electronic properties of SiC nanotubes

E. Chigo Anota, Gregorio Cocoletzi

Page range: 53-59

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Abstract

We have performed studies of the structural and electronic properties of functionalized single wall silicon carbide nanotubes (SW-SiCNTs) with chirality (5,5). Our first principles studies are done using density functional theory. The exchange-correlation energies are modeled according to the Hamprecht-Cohen-Tozer-Handy functional in the generalized gradient approximation (HCTH-GGA) and the DNP basis function with double polarization is applied. To determine the most stable geometry, we have applied the minimum energy criterion considering several initial configurations of the hydroxyl (OH) functional group interacting with the single wall SiCNT. In particular, we tested different orientations of the OH adsorbed on the nanotube surface (oriented towards the Si or C atoms) and at the end of the nanotube. Results indicate that the most favorable geometry corresponds to OH adsorption (chemisorption) at the end of the nanotube. The polarity increases yielding better conditions for solubility and dispersion. The work function of the SW-SiCNT-OH is reduced, which in turn favors conditions for field emission properties (FEPs). Finally, the presence of silicon or carbon mono-vacancies in the functionalized nanotubes suggests this may be a good structure to fabricate semiconductor devices

Open Access October 27, 2013

Spectroscopic analysis of pindolol irradiated in the solid state

Magdalena Ogrodowczyk, Barbara Marciniec, Piotr Kachlicki

Page range: 60-66

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Abstract

Pindolol ((2RS)-(1-(1H-indol-4-iloxy)-3- [(1-metyloetylo)amino]-2-propanol) in substantia was exposed to ionising radiation emitted by high energy electrons from an accelerator, in the standard sterilisation dose of 25 kGy and in higher doses from the range 50–400 kGy. The effects of irradiation were checked by spectrometric methods (UV, MS, FT-IR, EPR) and hyphenated methods (HPLC-MS) and the results were referred to those obtained for non-irradiated sample. EPR results indicated the presence of free radicals in irradiated samples, in the amount of 1.36 × 1016 spin g−1 for 25 kGy and 3.70×1016 spin g−1 for 400 kGy. The loss of pindolol content determined by HPLC was 1.34% after irradiation with 400 kGy, while the radiolytic yield of the total radiolysis for this dose of irradiation was 2.69×107 mol J−1. By means of HPLC-MS it was possible to separate and identify one product of radiolytic decomposition, which probably is 2-((R)-3-(1H-indol-4-yloxy)-2-hydroxypropylamino)propan-1-ol formed upon oxidation. In the range of sterilisation doses (25–50 kGy), pindolol was found to show high radiochemical stability and would probably be safely sterilised by the standard dose of 25 kGy.

Open Access October 27, 2013

Synthesis of 1-(pyrrolidin-2-ylmethyl)-1H-azoles and their piperidine-derived homologues

Sergey Zhersh, Oleksandr Karpenko, Vasyl Ripenko, Andrey Tolmachev, Oleksandr Grygorenko

Page range: 67-73

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Abstract

A convenient preparation of 1-(pyrrolidin-2-yl)-1H-pyrazoles, -imidazoles, and -1H-1,2,4-triazoles, 1-(piperidin-2-yl)-1H-pyrazoles and -1H-1,2,4-triazoles, and 1-(piperidin-3-yl)-1H-1,2,4-triazoles by alkylation of azoles (viz. pyrazoles, imidazoles, and triazoles) with N-Cbz-prolinol mesylate or its analogues and subsequent deprotection is reported. The two-step method allows for synthesis of the title compounds in 16–65% yields. The utility of the procedure has been demonstrated by multigram preparation of a 15-member building block mini-library for the lead-oriented synthesis of compound libraries. These building blocks perfectly fit the definition of low-molecular-weight hydrophilic three-dimensional templates, which leave much room for the lead-oriented synthesis of the compound libraries.

Open Access October 27, 2013

Stability prediction of Cu2+, Ni2+ and Zn2+ N-salicylidene-aminoacidato complexes by models based on connectivity index 3 χ v

Ante Miličević, Nenad Raos

Page range: 74-79

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Abstract

This paper presents models for the estimation of stability constants (K 1 and β 2) of nickel(II), copper(II) and zinc(II) mono- and bis-complexes with 5 Schiff bases (salicylideneglycine, salicylidenealanine, salicylideneserine, salicylidenephenylalanine, and salicylidenetyrosine). The models were based on the molecular-graph theory and valence molecular connectivity index of the 3rd order, 3χv , derived from it. Univariate linear models were developed for each metal separately, while in the common models for two and three metals, the indicator variable, In, was introduced. The standard error of models for the log K 1 constant was less than 0.12, while for log β 2 models, the S.E. did not exceed 0.14.

Open Access October 27, 2013

Stress degradation study of two oral antidiabetics, gliclazide and glipizide, and chemical analysis by LC and LC/MS methods

Anna Gumieniczek, Anna Berecka, Rafał Pietraś, Marek Ślebioda

Page range: 80-89

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Abstract

Kinetic study of degradation of two oral antidiabetics, gliclazide and glipizide, was performed using new HPLC method which was validated in terms of selectivity, sensitivity, linearity, precision and accuracy. The stress degradation was performed in 0.2 M HCl, 0.2 M NaOH as well as in acetate and phosphate buffers over the pH range 3.8–8.3 at 30 and 70°C. In strong acidic and alkaline media gliclazide was almost fully degraded while glipizide showed much higher stability. Generally, degradation processes of gliclazide and glipizide were observed as the first order reactions while the rates of decomposition for both drugs were smallest at pH 8.3. The samples of gliclazide and glipizide stressed in strong acid and alkali at 70°C were additionally analyzed using an LC/MS method and some products of decomposition were detected and identified. It was concluded that glipizide was more resistant to very high or very low pH and would have higher stability compared to gliclazide. Such comparisons have not been performed so far for these valuable drugs. Additional LC/MS study showed that during decomposition of sulfonylureas, different degradation pathways were possible.

Open Access October 27, 2013

Fullerenes patched by flowers with octagonal core

Raluca Pop, Mihai Medeleanu, Mircea Diudea, Beata Szefler, Jerzy Cioslowski

Page range: 90-97

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Abstract

The aromatic character of three different flowers of general formula [n:(p i,p j)n/2], namely [8:(5,7)4], [8:(6,6)4] and [8:(5,6)4], has been evaluated by means of geometric (HOMA index), energetic (heats of formation) and magnetic criteria (NICS index, exaltation of magnetic susceptibility). Also, the reactivity descriptors within the DFT approach -absolute hardness, electrophilicity, Fukui functions — have been computed. All the different methods used for estimating the aromaticity led to a unitary conclusion. Two fullerene structures, patched by the most stable 8-Sumanene flower, have been designed and evaluated by means of ab initio computations

Open Access October 27, 2013

Vortex-assisted ionic liquid based liquid-liquid microextraction of selected pesticides from a manufacturing wastewater sample

Tatjana Trtić-Petrović, Aleksandra Dimitrijević

Page range: 98-106

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Abstract

The ionic liquid based vortex-assisted liquid-liquid microextraction (IL-VALLME) procedure was developed and validated for determination of four pesticides in a manufacturing wastewater sample: acetamiprid, imidacloprid, linuron and tebufenozide. The following ILs were tested as extractants: 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-hexyl-3-methylimidazolium hexafluorophosphate, and 1-methyl-3-octylimidazolium hexafluorophosphate. The extraction efficiency and the enrichment factor dependencies on the type and amount of ionic liquids, extraction and centrifugation time, volume, pH and the ionic strength of the sample, were investigated. The concentration of pesticides in the aqueous and IL phases was determined by HPLC-DAD. The optimal conditions for extraction of the pesticides were determined: the aqueous sample volume of 10 mL with the addition of 0.58 g NaCl, 40 µL of the 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide as extractant, 2 min extraction under vigorous mixing applying the vortex agitator, and separation of the phases by centrifugation for 2 min at 1000 rpm. The calibration curves of the pesticides showed good linear relationship (r2 ≥ 0.9996) in the concentration range from 0.005 to 1.00 mg L−1. Determined LOD values are 1.8, 2.3, 4.8 and 8.6 µg L−1 for Tebf, Linr, Acet and Imid, respectively. The optimized IL-VALLME was applied for determination of the pesticides in the pesticide manufacturing wastewater.

Open Access October 27, 2013

Investigations of ternary complexes of Co(II) and Ni(II) with oxydiacetate anion and 1,10-phenanthroline or 2,2′-bipyridine in solutions

Dariusz Wyrzykowski, Joanna Pranczk, Dagmara Jacewicz, Aleksandra Tesmar, Bogusław Pilarski, Lech Chmurzyński

Page range: 107-114

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Abstract

Potentiometric (PT) and conductometric (CT) titration methods have been used to determine the stoichiometry and formation constants in water for a series of ternary complexes of Co(II) and Ni(II) involving the oxydiacetate anion (ODA) and 1,10-phenanthroline (phen) or 2,2′-bipyridine (bipy) ligands, namely [Co(ODA)(phen)(H2O)], [Co(ODA)(bpy)(H2O)], [Ni(ODA)(phen)(H2O)] and [Ni(ODA)(bpy)(H2O)]. The ternary complex formation process was found to take place in a stepwise manner in which the oxydiacetate ligand acts as a primary ligand and the phen or bipy ligands act as auxiliary ones. The stability of the ternary complexes formed is discussed in the relation to the corresponding binary ones. Furthermore, the kinetics of the substitution reactions of the aqua ligands in the coordination sphere of the Ni-ODA and Co-ODA complexes to phen or bipy were studied by the stopped-flow method. The kinetic measurements were performed in the 288–303 K temperature range, at a constant concentration of phen or bipy and at seven different concentrations of the binary complexes (4–7 mM). The influence of experimental conditions and the kind of the auxiliary ligands (phen/bipy) on the substitution rate was discussed.

Open Access October 27, 2013

Novel ion-binding C3 symmetric tripodal triazoles: synthesis and characterization

Gábor Neumajer, Gergő Tóth, Szabolcs Béni, Béla Noszál

Page range: 115-125

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Abstract

Novel C3 symmetric tripodal molecules were synthesized from cyclohexane 1,3,5-tricarboxylic acid. Utilizing click and Sonogashira reactions, ion-binding triazole and pyridazin-3(2H)-one units were incorporated to form polydentate ligands for ion complexation. The structures of the novel C3 symmetric derivatives were extensively characterized by 1H, 13C and 2D NMR techniques along with HRMS and IR. The copper(I)-binding potentials of these ligands were investigated by using them as additives in model copper(I)-catalysed azide-alkyne cycloaddition (CuAAC) reactions. The copper(I) complexation ability of our compound was also proved by different spectroscopic methods, such as mass spectrometry, UV and NMR spectroscopy. Based on the mass spectrometric data all of the C3 symmetric ligands formed 1:1 complex with copper(I) ion. The specific role of C3 symmetric polydentate form in the complexation process was also discussed

Open Access October 27, 2013

Photonic crystals obtained by soap-free emulsion terpolymerization

Edina Rusen, Aurel Diacon, Alexandra Mocanu

Page range: 126-130

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Abstract

This paper presents the use of soap-free emulsion terpolymerization to obtainphotonic crystals (PCs). Monodisperse latexes resulted from the polymerization of styrene (ST) with 2-hydroxyethyl methacrylate (HEMA) and acrylic acid (AA) at different compositions defined as system A, B and C respectively. The water solubility of the macroradicals determined different nucleation mechanisms in all three cases. The micellar nucleation mechanism was more predominant for generating system A, whereas the homogeneous nucleation was specific for system C. For system B, both nucleation mechanisms werepossible with the same probability. The latexes and the resulted PCs were characterized by optical microscopy (OM), dynamic light scattering (DLS), gel permeation chromatography (GPC) and UV-VIS spectroscopy.

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).

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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

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Catalysis Conferences
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Date: 1.02 - 3.02.2024
2nd International Summit on Biopolymers and Polymer Science
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Date: 17-19.06.2024
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Date: 1.07 – 2.07.2024
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