Search

The paper shows the possibilities of increasing the hydrophobicity of the paper surface by applying layers of hydrophobic material to the surface. Various application techniques and the following substances were tested: stearic acid, shellac and zinc-hydroxide. Hydrophobicity was tested using the modified Cobb method, measuring the contact angle and drop retention time. The presence of hydrophobizing agents was confirmed by FTIR spectroscopy. It was found that the methods of applying the hydrophobizing agent, used in this work, give much better results with stearic acid, compared to shellac. This manuscript presents novel possibilities of increasing paper surface hydrophobicity by applying layers of hydrophobic material to the surface. Various layer application techniques were examined, as well as substances including: stearic acid, shellac and zinc-hydroxide. Hydrophobicity was tested using the modified Cobb method, measuring the contact angle and drop retention time. The presence of hydrophobizing agents was confirmed by FTIR spectroscopy. Based on the results achieved, it can be concluded that the methods of applying the hydrophobizing agent, used in this work, give much better results with stearic acid, compared to shellac.

Polymer resins based on acrylates obtained from Bis-GMA (Bisphenol A glycide methacrylate), which is suitable for photopolymerization, are used in dentistry for various purposes due to the ease of application and the possibility to influence their properties by adding reinforcements of different shapes, crystal structure and chemical compositions. Reinforcement in the form of particles based on MgAlLDH (layered double hydroxide) deposited on silica obtained from rice husks on two substrates. A metal base and glass were used. The adhesive properties are important in order to see the possibility of using these materials in applications. In order to measure the adhesive properties of the material, the composite microhardness measurement method is used by applying different loads in order to evaluate the adhesion parameter that shows the effect of the coating on the substrate. It was compared to how a pure photopolymerizing acrylate matrix bonds with a chromium-based dental alloy substrate that is used in the production of different parts of dentures by bonding to a glass substrate. Then, it was compared how composite materials are bonded to both substrates. Adhesion was monitored through the change in wetting angle between the composites, and the results were compared with the results of microindentation. It was shown that the addition of composite particles increases the adhesive properties of the composite compared to the pure matrix and that better adhesion is achieved between the composite and the metal substrate than between the composite and the glass substrate.

The subject of this research is the production process of polyvinyl chloride (PVC) regranulate using a plasticizer synthesized from recycled poly(ethylene terephthalate) (PET). In this way, a plasticizer was synthesized that does not pose a risk to human health and the environment in accordance with the principles of chemical leasing and green chemistry. The obtained plasticizer was characterized using elemental analysis, FTIR, and NMR spectroscopy and determination of hydroxyl and acid number. The mechanical properties of materials obtained on the basis of recycled PVC and plasticizers from PET were tested according to standard methods.

From an industrial point of view, porous ceramics represent an important material, however, economically and technologically acceptable solutions are still being sought for its preparation. Porosity control is a key step in achieving the desired properties for a specific application. In order to obtain multiporous ceramics, in this work, kaolin clay and polystyrene beads were used as organic sacrificial phase. After mixing, the samples were sintered at 1050 oC for 1 h. Characterization included Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), X-ray diffraction analysis (XRPD), elemental CHNS analysis and compressive strength investigations. The analysis of the obtained results showed that hierarchically ordered, multiporous ceramics, with appropriate mechanical properties can be prepared in the presence of an organic component whose burnout during sintering leaves behind pores of different dimensions.

In this study, the petals collected from peony hybrid Paeonia lactiflora "Bowl of Beauty" and Calendula officinalis L. were extracted using an ethanol-water mixture assisted with microwave and ultrasonic treatment. The isolation of Calendula officinalis L. essential oil was done by hydrodistillation as well. The total phenolic and flavonoids content in the extracts and oil were determined and their antioxidant activity was evaluated. The highest total phenolic content was found for the extracts of hybrid P. lactiflora and C. officinalis L. obtained by ultrasound extraction (83.16 and 114.47 mg GA/g, respectively), while the flavonoid content obtained by microwave-assisted extraction was relatively high (123.48 and 65.29 mg QE/g, respectively). The highest antioxidant activity was obtained in DPPH• and ABTS•+ assay for the microwave-assisted extraction of hybrid P. lactiflora (79% and 83%) and ultrasound-assisted extraction of C. officinalis L. (45% and 49%), respectively. To improve antioxidant activity of both types of examined analytes (extracts and essential oil), the pectin biopolymer film (as a carrier) was prepared in the process of enzymatically assisted catalysis. Optical microscopy and FTIR spectroscopy were used for the characterization of obtained materials. The films, with essential oil of C. officinalis L. and gallic acid, showed significantly increased percentage inhibition in DPPH• and ABTS•+ test (91% and 95%, respectively) after 10 minutes. The results, also, showed that all formulations of pectin biopolymer film, modified with gallic acid, can be successfully applied as a carrier for both types of ingredients.

The subject of this study is the synthesis of glycolysates from recycled poly (ethylene terephthalate) (PET) by depolymerization using diethylene glycol (DEG) in the presence of catalyst FASCAT 4100. The resulting glycolysate was then treated with maleic anhydride and finally with 2-octanol to obtain a 2-EtHex/MA/DEG/PET/EG/MA/2-EtHex plasticizer. The characterization of the obtained plasticizer was performed by infrared spectroscopy with Fourier transform (FTIR) and NMR spectroscopy. The obtained plasticizers were mixed into bitumen with 10 wt. % and tests of mechanical properties of obtained products were performed.

The aim of this study was to investigate a possibility of synthesis of porous ceramics with controlled open porosity, which could be used as sorbents and catalyst supports. Two organic additives were used to obtain open porosity: polystyrene beads and cellulose fibers, which are mixed with kaolin clay powder and the appropriate water content. Samples were sintered at 1050°C for 1 h. Characterization of the obtained products included X-ray powder diffraction analysis (XRPD), Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and elemental CHNS analysis. In addition, porosity was examined by quantification of visual information. The specific surface areas were determined by the Brunauer–Emmett–Teller (BET) method. Also, density and compressive strength of the obtained samples were assessed. It was determined that by sintering, the organic component completely leaves the system. For samples prepared with polystyrene beads and with cellulose fibers, satisfactory mechanical properties were obtained: compressive strengths were 1.42 and 1.56 MPa, respectively. It was noted that significantly higher open porosity was obtained by using polystyrene beads as a sacrificial template (porosity of ~56 %) instead of cellulose fibers (porosity of ~6 %).

Rice husk was used to produce silica particles, which were then used to reinforce the polymer matrix. The synthesized SiO2 particles were characterized using X-ray diffraction, Fourier transforms infrared spectroscopy (FTIR) and scanning electron microscopy with EDS. In a PMMA matrix, prepared SiO2 particles in amounts of 1, 3, and 5 wt.% were used as reinforcing agents. The goal of this research was to see if SiO2 particles had any effect on the mechanical properties of polymer composite materials. The morphology of the composites was examined using a field emission scanning electron microscope (FE-SEM). Vickers microindentation hardness and impact testing were used to determine the mechanical properties of the obtained composites. The indentation creep’s behavior of a polymethylmetacrylate (PMMA) composite material with varying amounts of nanoparticles (SiO2) was investigated and analyzed.

In this study, the structure, morphology and composition of the synthesized magnetite/3D-printed wollastonite (3D_W/M) composite were characterized, and its adsorption performance with respect to As(V) and Cr(VI) were studied. Magnetite (MG) modified 3D printed wollastonite was obtained by two step procedure: modification of 3D_W with 3-aminoproylsilane (APTES) followed by controlled magnetite (MG) deposition to obtain 3D_W/M adsorbent. The structure/properties of 3D_W/M were confirmed by applying FTIR, XRD, TGD/DTA, and SEM analysis. The adsorption properties of hybrid adsorbents were carried out for As(V) and Cr(VI) removal - one relative to the initial pH value, the adsorbent mass, the temperature, and the adsorption time. Time-dependent adsorption study was best described by pseudo-second order equation, while Weber Morris analysis showed that intraparticle diffusion controled diffusional transport. Similar activation energy, 17.44 and 14.49 kJ•mol-1 for adsorption As(V) and Cr(VI) on 3D_W/M, respectively, indicated main contribution of physical adsorption. Determination of adsorption parameters was performed by applying different adsorption isotherm models, and the best fit was obtained using Freundlich model. The adsorption capacity of 24.16 and 29.6 mg g-1 for As(V) and Cr(VI) at 2ºC, Co = 5.5 and 5.3 mg L-1, respectively, were obtained. Thermodynamic study indicated favourable process at a higher temperature. Preliminary fixed-bed column study and results fitting with Bohart-Adams, Yoon-Nelson, Thomas, and Modified dose-response model showed good agreement with results from the batch study.

Magnetite (MG) modified cellulose membrane (Cell-MG), obtained by reaction of 3-aminosilane and subsequently with diethylenetriaminepentaacetic acid dianhydride functionalized waste Cell fibers (Cell-NH2 and Cell-DTPA, respectively), and amino-modified diatomite was used for Azoxystrobin and Iprodione removal from water. Cell-MG membrane was structurally and morphologically characterized using FT-IR and FE-SEM techniques. The influences of operational parameters, i.e. pH, contact time, temperature, and the mass of adsorbent on adsorption and kinetics were studied in a batch system. The calculated capacities of 35.32 and 30.16 mg g-1 for Azoxystrobin and Iprodione, respectively, were obtained from non-linear Langmuir model fitting. Weber-Morris model fitting indicates the main contribution of intra-particle diffusion to overall mass transport resistance. Thermodynamic data indicate spontaneous and endothermic adsorption. The reusability of adsorbent and results from wastewater purification showed that Cell-MG could be used as general-purpose adsorbent. The adsorbent/adsorbate surface interaction was considered from the results obtained using density functional theory (DFT) and calculation of molecular electrostatic potential (MEP). Thus, a better understanding of the relation between the adsorption performances and contribution of non-specific and specific interactions to adsorption performances and design of novel adsorbent with improved properties was deduced

Thermal properties of acrylate-based composite combined with alumina-based particles were investigated. The composites were made of poly (methyl methacrylate) (PMMA) modified with dimethyl itaconate (DMI) as a matrix. Neat alumina particles (Al2O3) and alumina doped with iron oxide (Al2O3-Fe) modified with 3-aminopropyl-trimethoxylane (AM) and flax oil fatty acid methyl esters (biodiesel - BD) were used as reinforcement. Thermal conductivity measurements showed that composite with alumina particles with the highest alpha phase content had the highest thermal conductivity values. Mechanical properties (tensile strength, modulus of elasticity and elongation at break) were improved by the addition of modified alumina particles to PMMA/DMI matrix. The thermal properties are the most improved for composite with 3 wt.% Al2O3-Fe-AM particles that had the lowest temperature in a crack zone was noticed (10.28 %) compared to PMMA added due to the better stiffness and highest thermal conductivity.

The derivatives of isatin have already been known to display a variety of biological activities. Therefore, the studies on their activity and its relation to structure have recently become a popular subject for investigation. The examined compounds were synthesized by the reaction of isatin and substituted primary amines and characterized by spectroscopic methods. The investigation of the antimicrobial and antioxidative activity of the synthesized compounds was performed by broth microdilution method. As for the characterization of the investigated isatin based Schiff bases, the linear solvation energy relationships (LSER) were used to analyze the solvent influence on the UV absorption maxima shifts (max), using the well known Kamlet–Taft model and taking geometrical isomers into consideration when possible. Linear free energy relationships (LFER) were used to analyze substituent effect on pKa, as well as NMR chemical shifts and max values. The antimicrobial activity and characterization were related using both experimental and theoretical methods. [Project of the Serbian Ministry of Education, Science and Technological Development, Grant no. 172013]

Two-step synthesis of Fe2O3 particles, performed by precipitation from iron(III) chloride (FeCl3•6H2O) using ammonium hydroxide in first step and calcination at 400 and 700°C during 4 h, provided Fe2O3 400°C and Fe2O3 700°C photocatalysts, respectively. The electrospinning process was used to prepare iron oxide fibers, named Fe2O3 fiber. Morphological and structural properties of samples were determined by Scanning Electron Microscopy (SEM), X-ray diffraction (XRD), Fourier Transform Infra-Red (FT-IR) and BET/BJH analysis. It was found that the α-Fe2O3 phase (hematite) has shown the compaction of the structure at 700°C, i.e. lower textural properties. Hematite particles and fibers are used for bisphenol A (BPA) removal by photocatalytic decomposition and the enhanced catalytic performance was found with the use of Fe2O3 400°C particles. [Project of the Serbian Ministry of Education, Science and Technological Development, Grant no. TR34011]

Commercial alumina wiskers (Al2O3 w) and synthesized alumina particles via sol-gel technique (Al2O3 m) were used as reinforcement in unsaturated polyester resins (UPR). Composite materials with the addition of 0.1 wt. %, 0.25 wt. %, 0.5 wt. %, 1.0 wt. %. i 2.5 wt. % of alumina based particles were obtained. Structural analysis of used alumina reinforcement and obtained UPR/Al2O3 composites was performed by FTIR spectroscopy. Morphology was studied by scanning electron microscopy (SEM). The microhardness test was done using the Vikers method. Obtained results showed an increase of microhardness of UPR/Al2O3 w composites up to 66.4%, while the increase of microhardness of UPR/Al2O3 m composite was up to 52.3% compared to UPR matrix.

A novel double layered hybrid materials, consisting of low density polyethylene (LDPE) base layer and polycaprolactone (PCL) top layer containing surface modified nanocellulose (NC) based nanocomposites in 0.5 and 2 % loadings, were studied in order to design multipurpose packaging material. NC was covalently modified with maleic anhydride (MA) to obtain NCMA, and upon co-precipitation of copper (II) oxide (CuO) on NC and NCMA surface, NC-CuO and NCMA-CuO nanocomposite materials were produced. Two drying methods, conventional and lyophilization, were applied to investigate process influences on the properties of obtained hybrid material. Oxygen transmission rate and antimicrobial activity were determined for all produced hybrid materials. PE-PCL-NCMA-CuO-L2 exhibited the highest antifungal properties, indicating contribution of MA residual group and drying conditions (liophylisation) to achievement of 97 % reduction in cell viability of C. albicans. The sample with 2 % of NCMA-CuO, PE-PCL-NCMA-CuO2, demonstrated to be the most promising material regarding improvement in antibacterial and antifugal activity, as well as 16 % lower value of the oxygen transmission rate in comparison to pure LDPE. [Project of the Serbian Ministry of Education, Science and Technological Development, Grant no. III45019]

The substituent and solvent effects on solvatochromism in 3-[(4-substituted) phenylamino]isobenzofuran-1(3H)-ones were studied using experimental and theoretical methodologies. The effect of specific and non-specific solvent–solute interactions on the shifts of UV–Vis absorption maxima were evaluated using the Kamlet–Taft and Catalán solvent parameter sets. The experimental results were studied by density functional theory (DT) and time-dependent density functional theory (TD-DFT). The HOMO/LUMO energies (EHOMO/ELUMO) and energy gap (Egap) values, as well as the mechanism of electronic excitations and the changes in the electron density distribution in both ground and excited states of the investigated molecules were studied by calculation in the gas phase. The electronic excitations were calculated by the TD-DFT method in the solvent methanol. It was found that both substituents and solvents influence the degree of π-electron conjugation of the synthesized molecules and affect the intramolecular charge transfer character. [Project of the Serbian Ministry of Education, Science and Technological Development, Grant no. 172013]

This paper presents the optimized technological process for obtaining stable calcium carbonate dispersion (CaCO3) in accordance to the standard prescribed in the paper industry. The reason for using CaCO3 in paper production is their low price when compared to the cellulose fibers and its ability to improve the properties of the final product. However, CaCO3 is alkaline filler that has relatively poor chemical stability that may affect the characteristics of the paper. For this reasons it is necessary to optimize the technology for obtaining a stable dispersion of CaCO3 with particles diameter in range 1 mm

In presented paper, influence of temperature, precursor concentration and different hydroxides on properties of activated carbon obtained from saccharose were investigated. The samples were prepared by hydrothermal treatment and activated using KOH, NaOH and LiOH. Two saccharose concentrations (0.5, 1.0 mol/dm3) and three temperatures (160, 200, 240 ºC) were changed in hydrothermal treatment. Activation processes were performed at 750ºC under N2 atmosphere. Samples were characterized by X-ray powder diffractometry, elemental analysis, N2 adsorption-desorption measurements, Fourier-transform infrared spectrometry, scanning electron microscopy and thermal analysis. The obtained samples were tested for potential application in dyes removal from water solutions. [Project of the Serbian Ministry of Education, Science and Technological Development, Grant no. III45005, Grant no. III45012 and Grant no. TR34013]

The multistage synthesis of the multi-wall carbon nanotubes (MWCNT) modified with polyamidoamine dendrimers, A1/ and A2/MWCNT, capable of cation removal, is presented in this work, as well as novel adsorbents based on these precursor materials and modified with goethite nano-deposit, α-FeOOH, A1/ and A2/MWCNT–α-FeO(OH) adsorbents used for As(V) removal. In a batch test, the influence of pH, contact time, initial ion concentration and temperature on adsorption efficiency were studied. Adsorption data modelling by the Langmuir isotherm, revealed good adsorption capacities (in mg g-1) of 18.8 for As(V) and 60.1 and 44.2 for Pb2+ and Cd2+ on A2/MWCNT, respectively. Also, 27.6 and 29.8 mg g-1 of As(V) on A1/ and A2/MWCNT–α-FeO(OH), respectively, were removed. Thermodynamic parameters showed that the adsorption is spontaneous and endothermic processes. Results of the study of influences of competitive ions: bicarbonate, sulfate, phosphate, silicate, chromate, fluoride and natural organic matter (NOM), i.e., humic acid (HA), showed the highest effect of phosphate on the decrease of arsenate adsorption. Time-dependent adsorption was best described by pseudo-second-order kinetic model and Weber–Morris model which predicted intra-particle diffusion as a rate-controlling step. Also, activation energy (Ea / kJ mol-1): 8.85 for Cd2+, 9.25 for Pb2+ and 7.98 for As(V), were obtained from kinetic data. [Project of the Serbian Ministry of Education, Science and Technological Development, Grant no. III45019 and Grant no. OI 172057]

Fourteen mono- and bis-carbohydrazone ligands have been synthesized and characterized. Antioxidant activity of the substances was investigated together with possible (E)/(Z) isomerization, and explained on the most active antioxidant compound 4 in various dimethyl sulphoxide–water mixtures. The addition of water to the system was involved in the formation of hydrated molecules which was confirmed in NMR after the addition of D2O. The ligands were tested in vitro against Gram-positive and Gram-negative bacteria and fungi, and their activity was discussed in relation to the structure of investigated carbohydrazone. [Project of the Serbian Ministry of Education, Science and Technological Development, Grant no. 172013]

The morphological, thermal and barrier properties of low-density polyethylene/polycaprolactone-modified nanocellulose hybrid materials were investigated in this paper. Nanonocelulose/magnetite (NC-Fe3O4) nanocomposite and maleic acid functionalized NC/magnetite (NCMA-Fe3O4) nanocomposite were prepared and used as filler at various concentrations (5, 10 and 15 wt. %) in polycaprolactone (PCL) layer. PE was coated with PCL/NC/magnetite layer. The addition of the filler did not unfavorably affect the inherent properties of the polymer, especially its barrier properties. Oxygen permeation measurements show that the oxygen barrier properties of magnetite enriched PCL film were improved due to chemical activity of added material. The highest level of barrier capacity was observed for PE samples coated with PCL based composite with NCMA-Fe3O4 micro/-nanofiller, which implies the significant contribution of nanocellulose surface modification with maleic anhydride residue to improved barrier properties. [Projekat Ministarstva nauke Republike Srbije, br. III45019 i br. OI172013]

The present study reports the new facile methodology for synthesis of symmetrical and asymmetrical thioureas by an one-pot reaction of amine, carbon disulfide and oxidants: hydrogen peroxide, ethylenediamine tetraacetic acid (EDTA)/sodium percarbonate system or air. The structures of the synthesized compounds were confirmed by IR, 1H and 13C NMR and MS methods. Reaction mechanism has been proposed on the basis of reaction intermediate isolation and their structure determination. The synthetic benefits of the presented methods is reflected in the operational simplicity, mild reaction conditions, short reaction times, recycling of solvent, high purity and yield of products, absence of dangerous by-products and technological applicability at industrial scale. Considering commercial importance of the thioureas, it can be emphasized that implementation of the optimal synthesis of thiourea, based on presented methods, at industrial level of production would provide concurrent alternative to existing technologies in use. [Projekat Ministarstva nauke Republike Srbije, br. 172013]

A novel adsorbents NC-PEG, obtained by the modification of nanocellulose (NC) with PEG-6-arm amino polyethylene glycol (PEG-NH2) via maleic anhydride (MA) linker, was used for the removal of Cd2+ and Ni2+ from water. Subsequent precipitation of goethite (FO) on NC-PEG produced NC-PEG/FO adsorbent which was used for As(V) and As(III) removal. In a batch test, the influence of pH, contact time, initial ion concentration and temperature on adsorption efficiency were studied. The maximum adsorption capacities found for Cd2+ and Ni2+, obtained by the use of Langmuir model, were 37.9 and 32.4 mg g−1 at 25 °C, respectively. Also, high As(V) and As(III) removal capacity of 26.0 and 23.6 mg g-1 were obtained. Thermodynamic parameters indicate endothermic, feasible and spontaneous nature of adsorption process. Kinetic study, i.e. fitting by Weber-Morris model predicted intra-particle diffusion as a rate-controlling step. Multi-cycle reusability of both NC-PEG and NC-PEG/FO, significantly affects the affordability of techno-economic indicators for consideration of their possible application. [Ministry of Education, Science and Technological developments of the Republic of Serbia, Project No. 172013, and University of Defence, Republic of Serbia, project VA-TT/4/16-18]

In this paper, the impact of wood fiber surface modification on mechanical properties of poly-(methyl methacrylate)(PMMA)-wood composite was examined. FTIR analysis has shown that the wood fiber surface modification was accomplished and that the matrix-fiber bond was established. The SEM image of the breakage surface has affirmed the improved adhesion between the fibers and the polymer in the specimen with modified wood fibers. The bond improvement between the wood fibers and the matrix results in increased hardness and a better distribution of strain within the composite. High speed impact testing results have shown that the specimen with the bonding agent can increase the absorbed energy six times when compared to the pure PMMA specimen.

The derivatives of isatin have already been reported to show a variety of biological activities. However, there has been no report on solvatochromic effect of isatin derivatives so far, and that could be of interest to study and relate to their electronic structure, as a part of the characterisation of these compounds. Linear solvation energy relationships (LSER) were used to analyze solvent influence on the UV absorption maxima shifts of investigated isatin derivatives, i.e. isatin based Schiff bases, by using Kamlet-Taft model. Linear free energy relationships (LFER) were applied to the substituent-induced NMR chemical shifts (SCS) using SSP (single substituent parameter). The obtained correlations together with theoretical calculations gave insight into the influence of the molecular conformation on the transmission of substituent effects, as well as on solute/solvent interactions. The molecular electrostatic potential (MEP) surface map was plotted over the optimized geometry of the molecules in order to visualize electron density distribution and explain origin of solvent/solute interactions. [Projekat Ministarstva nauke Republike Srbije, br. 172013]

2-Pyridones are important heterocyclic compounds that are widely used in medical chemistry, and their various derivatives have significant biological and medical applications. In this paper, the synthesis of 2-pyridones as well as 2-pyridone based compounds such as 2-quinolones using microwave assisted organic chemistry is reviewed. The review is divided in three parts. In the first part, microwave synthesis of 2-pyridones according to the type of condensation is discussed. In the second part, microwave assisted synthesis of 2-quionolones is listed. At the end of the review several examples of microwave synthesis of other 2-pyridone based compounds (ring fused N-substituted 2-pyridones) are given. [Projekat Ministarstva nauke Republike Srbije, br. 172013]

The ultraviolet absorption spectra of the carboxyl group of three isomeric pyridine carboxylic acids N-oxides (picolinic acid N-oxide, nicotinic acid N-oxide and isonicotinic acid N-oxide) were determined in fourteen solvents in the wavelength range from 200 to 400 nm. The position of the absorption maxima (λmax) of the examined acids showed that the ultraviolet absorption maximum wavelengths of picolinic acid N-oxide are the shortest, and those of isonicotinic acid N-oxide acid are the longest. In order to analyze the solvent effect on the obtained absorption spectra, the ultraviolet absorption frequencies of the electronic transitions in the carboxylic group of the examined acids were correlated using a total solvatochromic equation of the form max = v0 + sπ + aα+ bβ, where υmax is the absorption frequency (1/λmax), p is a measure of the solvent polarity, β represents the scale of solvent hydrogen bond acceptor basicities and α represent the scale of solvent hydrogen bond donor acidities. The correlation of the spectroscopic data was carried out by means of multiple linear regression analysis. The solvent effects on the ultraviolet absorption maximums of the examined acids were discussed.

Linear free energy relationships (LFER) were applied to the IR, 1H and 13C NMR spectral data of N-(substituted phenyl)-2-cyanoacetamides. A variety of substituents were employed for phenyl substitution and fairly good correlations were obtained using the simple Hammett and the Hammett-Taft dual substituent parameter equations. The correlation results of the substituent induced 13C NMR chemical shifts (SCS) of the C1, C=O and N-H atom indicated different sensitivity with respect to electronic substituent effects. A better correlation of the SCSC=O with a combination of electrophilic and nucleophilic substituent constants indicated a significant contribution of extended resonance interaction (π-delocalization) within the π1-unit. The conformations of the investigated compounds were studied using the DFT B3LYP/6-311G method and, together with the results of 13C NMR and IR spectroscopic studies, a better insight into the influence of such a structure on the transmission of electronic substituent effects was obtained.

In the last three or four decades disperse dyes derived from pyridones (in particular azo pyridone dyes) have gained in importance, and are widely used in various fields. These compounds have excellent coloration properties, and are suitable for the dyeing of polyester fabrics. Basic features of these dyes are simplicity of their synthesis by diazotation and azo coupling. They generally have high molar extinction coefficient with medium to high light and wet fastness. The absorption maxima of these dyes show their visible absorption wavelength ranging from yellow to orange, which can be attributed to poorly delocalized electrons in the pyridone ring. However, there are several dyes with deep colors such as red or violet. Pyridone dyes with alkyl and aryl groups in ortho position to azo group show 2-pyridone/2-hydroxypyridine tautomerism, while those containing OH and NHR groups conjugated with the azo group show azo-hydrazone tautomerism. Determining azo-hydrazone tautomerism could be therefore interesting, since the tautomers have different physico-chemical properties and most importantly different coloration. The literature on azo-hydrazone tautomerism, determination of equilibrium position, and investigation of substituent and solvent influence on tautomerism has been summarized in the presented review. The general conclusion is that the equilibrium between two tautomers is influenced by the structure of the compounds and by the solvents used. The tautomeric behavior patterns of the arylazo pyridone dyes in the reviewed literature has been studied using various instrumental techniques, including FT-IR, UV-vis, and NMR spectroscopy. The quantum chemical calculations related to the azo-hydrazon tautomerism have also been included. A large number of pyridone dyes exist in hydrazone form in solid state, while in solvents there is a mixture of tautomers. In addition, the X-ray single-crystal diffraction data analysis of some commercial pyridone dyes has been discussed concluding that they all crystallize in the hydrazone form.

Spherical TiO2 particles of different size were dispersed in alkyd resin based on soybean oil. Four samples of TiO2 particles were used, three commercial and one obtained by acid catalyzed hydrolysis of titanium tetraisopropoxide. The size of the synthesized nanoparticles was determined by transmission electron microscopy. Surface modification of TiO2 nanoparticles was performed with propyl gallate and lauryl gallate. The influence of the size of TiO2 nanoparticles, their concentration and type of the surface modification on the rheological properties of alkyd resin was investigated. The obtained results have shown that the viscosity of the prepared dispersions was higher than viscosity of the pure resin, it increases with decreasing particle diameter and decreases with frequency increase. Surface modified particles showed higher influence on the viscosity of alkyd resin than unmodified, because their hydrodynamic volume is higher due to the presence of the adsorbed gallates, leading to the increase of effective volume fraction of particles in dispersion. For the lowest TiO2 concentration, the viscosity was higher for sample modified with lauryl gallate, due to the higher thickness of the adsorbed layer. The increase of concentration, because of less dispersion stability of the particles modified with propyl gallate, leads to particles agglomeration. The presence of agglomerates, which was confirmed by a change in the slope of the functional dependence of storage modulus on loss modulus, leads to a rapid increase in viscosity. [Projekat Ministarstva nauke Republike Srbije, br. 172062 i br. 45020]

Composites based on unsaturated polyester (UPe) resins and fumed silica AEROSIL® RY 50, NY 50, RX 50 and NAX 50, as well as graphite, TiO2 or organically modified clay CLOISITE 30B were prepared in order to investigate the influence of reinforcing agents on the mechanical properties of composites. Unsaturated polyester resins were synthesized from maleic anhydride and products of glycolysis, obtained by depolymerization of poly(ethylene terephthalate) with dipropylene glycol (UPe1 resin) and triethylene glycol (UPe2 resin) in the presence of tetrabutyl titanate catalyst. The obtained unsaturated polyesters were characterized by FTIR spectroscopy, acid and hydroxyl values, and their mechanical properties were also examined. Significant increase of the tensile modulus, tensile strength and decrease of the elongation at break was observed for composites prepared after addition of 10 wt.% of graphite or 10 wt.% of TiO2 to the UPe resins, indicating strong interaction between matrix and filler particles. On the other hand, nanocomposites prepared using UPe2 and hydrophobically modified silica nanoparticles showed lower tensile strength and tensile modulus than polymer matrix. The presence of CLOISITE 30B had no significant influence on the mechanical properties of UPe1, while tensile strength and tensile modulus of UPe2 increased after adding 10 wt.% of clay. [Projekat Ministarstva nauke Republike Srbije, br. 172013]

A new optimized laboratory synthesis of tetraalkyl thiuram disulfides, starting from dialkyl amines and carbon disulfide in presence of three oxidants (hydrogen peroxide, potassium peroxodisulfate and sodium hypochlorite) and appropriate reaction medium: two mixtures of isopropyl alcohol - water used in two consecutive syntheses, was presented in this work. First synthesis was performed in a recycled azeotropic mixture of isopropyl alcohol - water 87.7% - 12.3%, and second in a filtrate obtained after first synthesis, which was a mixture of isopropyl alcohol - water 70.4% - 29.6%. After the second synthesis and filtration, recycled azeotropic mixture isopropyl alcohol - water 87.7% - 12.3% was regenerated from the filtrate by rectification. Considering this, the technology for beneficial use of recycling isopropyl alcohol - water mixture as reaction medium for tetraalkyl thiuram disulfides synthesis was developed. Such concept contributes to extraordinary economical benefit of implemented optimal laboratory synthesis at semi-industrial level. High yields of tetraalkyl thiuram disulfides syntheses were obtained at both laboratory and semiindustrial level. Structure and purity of synthesized compounds were confirmed by elemental analysis, as well as FTIR, 1H and 13C NMR, and MS spectral data.

A simple and efficient method for separation and determination of dimethylarsenate DMAs(V) was developed in this work. Two resins, a strong base anion exchange (SBAE) resin and iron-oxide coated hybrid (HY) resin were tested. By simple adjusting pH value of water at 7.00, DMAs(V) passed through the HY column without any changes, while all other arsenic species [inorganic arsenic and monomethylarsonate, MMAs(V)] were quantitatively bonded on HY resin. The resin capacity was calculated according to the breakthrough points in a fixed bed flow system. At pH 7.00 the HY resins bonded more than 4150 μg g-1 of As(III), 3500 μg g-1 of As(V) and 1500 μg g1 of MMAs(V). Arsenic adsorption behavior in the presence of impurities showed tolerance with the respect to potential interference of anions commonly found in natural water. DMAs(V) was determined in the effluent by ICP-MS. The detection limit was 0.03 μg L?1 and relative standard deviation (RSD) was between 1.1?7.5 %. Proposed method was established performing standard procedures: with external standard, certified reference material and the standard addition method.

Protic and aprotic solvent effects on the reactivity of picolinic, nicotinic and isonicotinic acid, as well as of some substituted nicotinic acids with diazodiphenylmethane (DDM) were investigated. In order to explain the kinetic results through solvent effects, the second-order rate constants for the reaction of the examined acids with DDM were correlated using the Kamlet-Taft solvatochromic equation. The correlations of the kinetic data were carried out by means of the multiple linear regression analysis and the solvent effects on the reaction rates were analyzed in terms of the contributions of the initial and the transition state. The signs of the equation coefficients support the already known reaction mechanism. The solvatation models for all the investigated acids are suggested and related to their specific structure.

The Hammett correlations between 13C-NMR chemical shifts of the azomethine carbon atom and the corresponding substituent constants for thirtheen Schiff bases were established. Successful correlation of the chemical shifts with electrophilic substituent constants ó+ indicate significant resonance interaction of the substituents on the aniline ring with the azomethine carbon atom in the examined series of imines. The demand for electrons in the investigated compounds was compared to that of the N-benzylidenanilines and N-(phenyl substituted) pyridinealdimines. The way of transmission of the substituent effects was discussed and they are separated into resonance and inductive effects. Inductive effects prevail over resonance effects.

A optimized synthesis of N-alkyl, N,N-dialkyl- and N-cycloalkyl-O-isobutyl thioncarbamates by aminolysis of sodium isobutylxanthogenic acid (NaiBXAc) and primary, secondary and cycloalkyl amines was developed at laboratory scale and applied at semi-industrial level. Studies on dependence of N-n-propyl-O-isopropylthiocarbamate yield and purity with respect to reaction parameters: reaction time and molar ratio of n-propylamine and NaiBXAc, were performed. In such way, optimal reaction conditions for synthesis of N-alkyl, N,N-dialkyl- and N-cycloalkyl-O-isobutyl thioncarbamates, by aminolysis of NaiBXAc, were established. Also, comparative results of thioncarbamates synthesis starting from potassium isobutyl xanthate (KiBX) and corresponding amines in presence of different oxidants: hydrogen peroxide, sodium hypochlorite and new oxidative agent potassium peroxodisulfate were evaluated. Synthesized compounds have been fully characterized by FTIR, 1H and 13C NMR and MS data, elemental analysis and purity have been determined by gas chromatographic method (GC). According to our knowledge, ten synthesized thioncarbamates are for the first time characterized. Synthesized compounds could be used as selective reagents for flotation of copper and zinc ores. The presented methods offer several benefits, namely, high product yields and purity, simple operation, mild reaction conditions without use of hazardous organic solvents, while some of them could be implemented on industrial scale production.

The discovery of carbon nanotubes (CNTs) has opened a new door in nanotechnology. With their high surface area, unique electronic, thermal and mechanical properties, CNTs have been widely used as carriers for protein immobilization. In fact, carbon nanotubes present ideal support system without diffusional limitations, and also have the possibility of surface covalent functionalization. It is usually the oxidation process that introduces carboxylic acid groups. Enzymes and other proteins could be adsorbed or covalently attached onto carbon nanotubes. Adsorption of enzyme is a very simple and inexpensive immobilization method and there are no chemical changes of the protein. It has also been found that this technique does not alter structure and unique properties of nanotubes. However, a major problem in process designing is relatively low stability of immobilized protein and desorption from the carrier. On the other hand, while covalent immobilization provides durable attachment the oxidation process can reduce mechanical and electronic properties of carbon nanotubes. It can also affect the active site of enzyme and cause the loss of enzyme activity. Bioimmobilization studies have showed that there are strong interactions between carbon nanotubes surface and protein. The retention of enzyme structure and activity is critical for their application and it is of fundamental interest to understand the nature of these interactions. Atomic force microscopy (AFM), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and circular dichroism (CD) spectroscopy provide an insight into the structural changes that occur during the immobilization. The aim of this paper is to summarize progress of protein immobilization onto carbon nanotubes.

Over 50% of all colorants which are used nowdays are azo dyes and pigments, and among them arylazo pyridone dyes (and pigments) have became of interest in last several decades due to the high molar extinction coefficient, and the medium to high light and wet fastness properties. They find application generally as disperse dyes. The importance of disperse dyes increased in the 1970s and 1980s due to the use of polyester and nylon as the main synthetic fibers. Also, disperse dyes were used rapidly since 1970 in inks for the heat-transfer printing of polyester. The main synthetic route for the preparation of azo dyes is coupling reaction between an aromatic diazo compound and a coupling component. Of all dyes manufactured, about 60% are produced by this reaction. Arylazo pyridone dyes can be prepared from pyridone moiety as a coupling component, where substituent can be on nitrogen, and diazonim salts which can be derived from different substituted anilines or other heterocyclic derivatives. In addition, arylazo dyes containing pyridone ring can be prepared from arylazo diketones or arylazo ketoesters (obtained by coupling β-diketones or β-ketoesters with diazonim salts) by condensation with cyanoacetamide. Disazo dyes can be prepared by tetrazotizing a dianiline and coupling it with a pyridone or by diazotizing aniline and coupling it with a dipyridone. Trisazo dyes can be also prepared by diazotizing of aniline and coupling it with a tripyridone or by hexazotizing a trianiline and coupling it with a pyridone. The main goal of this paper is to give a brief review on the synthesis of arylazo pyridone dyes due to the lack of such reviews. In addition, some properties of arylazo pyridone dyes as light fastness and azo-hydrazon tautomerism are disccused.

Phencyclidine (PCP) or 1-phenyl-cyclohexylpiperidine is the best known representative drug from the compound class of arylcyclohexylamines. On an account of pharmacological activities it belongs to the family of drugs known as a dissociative anesthetics. In recent years, great attention has been paid to the investigation of the substances that have been abused, including PCP. PCP is the synthetic drug with stimulant and hallucinogens effects (street name “angel dust”) and it's situated on the Schedule Substances List, in Serbia and worldwide. In the beginning, PCP has been sold in pharmacies as local anesthetic, but very quickly it was pulled from sale because of the unwanted effects on consumer´s health causing psychoactive addiction. Taking into the account that today a great attention has been given to the substances that are subject of abuse, in this paper, biological and pharmacological effect of PCP and it's derivative is described. It is shown that PCP is antagonist of N-methyl-D-aspartate (NMDA) and that it causes antiglutamateric hallucinations. Unlike BTCP which agonist is NMDA receptor and is obtained by modifying the structure of PCP. This paper presents a PCP metabolism and provides an overview of the methods for their identification and quantification in the biological samples. Immunological tests of PCP in the biological samples can provide a quick but wrong result because of the possible interference with the other substances of abuse as opposed to instrumental methods. Based on the presented method and the results it was concluded that the method of choice for the examinations of biological samples for the presence of PCP is gas chromatography in combination with mass spectroscopy.

A synthesis of N-alkyl and N,N-dialkyl-O-ethyl and O-isopropyl thiocarbamates by oxidation of ammonium salt of ethyl and isopropylxanthogenic acid in a presence of sodium hypochlorite and hydrogen peroxide were performed. Ammonium salt of ethyl and isopropylxanthogenic acid was obtained by the reaction of alkylammonium sulfate and sodium ethyl and isopropyl xanthate. Studies on a dependence of N-ethyl-O-isopropylthiocarbamate yield and purity with respect to reaction parameters (reaction time, molar ratio of oxidant and ethylamonium salt of isopropylxanthogenic acid) were performed. Optimal reaction conditions for synthesis of N-alkyl and N,N-dialkyl-O-ethyl and O-isopropyl thiocarbamates were established. Synthesized compounds have been fully characterized by FTIR, 1H NMR and MS data, while purity has been determined by GC method. A plausible pathway for the N-alkyl and N,N-dialkyl-O-ethyl and O-isopropyl thiocarbamates synthesis, in the presence of the oxidative agents sodium hypochlorite and hydrogen peroxide, was proposed. The presented synthetic methods has been developed at laboratory and applied at semi-industrial level. The developed optimal method provides a powerful and versatile method for the preparation of N-alkyl and N,N-dialkyl-O-ethyl and O-isopropyl thiocarbamates. This new optimized method offer several benefits, namely, simple operation, mild reaction conditions, bypass of hazardous organic solvents, moderately toxic and inexpensive reagents, and also short reaction times and high product yields.

Twelve 3-cyano-4-(substituted phenyl)-6-phenyl-2(1H)-pyridinones were investigated by tandem mass spectrometry using positive as well as negative electrospray ionization. The influence of the electron affinity of the substituent and the steric effect on the fragmentation is discussed. Pyridinones with a substituent of low proton affinity show loss of water, HCN or benzene from the pyridinone ring in the first step of MS2 fragmentations. Oppositely, if a substituent with high proton affinity is present on the phenyl ring in the 4-position of pyridinone, the fragmentation paths are complex, depending mainly on the substituent proton acceptor ability. Elimination of neutral molecules CO, HCN, H2O, PhH (benzene) or Ph and CN radicals are fragmentation processes common for all compounds in the subsequent steps of the fragmentations.

The rate constants for the reactions of diazodiphenylmethane (DDM) with 6-substituted nicotinic acids in aprotic solvents at 30°C were determined. The obtained second order rate constants in aprotic solvents, together with literature data for benzoic and nicotinic acids in protic solvents, were used for the calculation of solvent effects, employing the Kamlet-Taft solvatochromic equation (linear solvation energy relationship - LSER) in the form: log k = log k0 + + sΠ*+ aα + bβ. The correlations of the kinetic data were performed by means of multiple linear regression analysis taking appropriate solvent parameters. The sign of the equation coefficients (s, a and b) were in agreement with the postulated reaction mechanism, and the mode of the solvent influences on the reaction rate is discussed based on the correlation results. A similar contribution of the non-specific solvent effect and electrophilic solvation was observed for all acids, while the highest contribution of nucleophilic solvation was influenced by their high acidity. Correlation analysis of the rate data with substituent óp parameters in an appropriate solvent using the Hammett equation was also performed. The substituent effect on the acid reactivity was higher in aprotic solvents of higher dipolarity/polarizability. The mode of the transmission of the substituent effect is discussed in light of the contribution of solute-solvent interaction on the acid reactivity.

The 13C- and 1H-NMR chemical shifts of thirteen N(1)-(4-substituted phenyl)-3-cyano-4,6-dimethyl-2-pyridones were measured in deuterated dimethyl sulfoxide (DMSO-d6). The correlation analysis for the substituent-induced chemical shifts (SCS) with σp, inductive (σI) and different scale of resonance (σR) parameters were performed using the SSP (single substituent parameter), DSP (dual substituent parameter) and DSP-NLR (dual substituent parameter-non-linear resonance) methods. The results of the calculations concerning the polar and resonance effects satisfactorily describe the substituent effects at the carbon atoms of interest. The mode of transmission of the substituent effects, both inductive and resonance, in relation to the geometry of the investigated pyridones is discussed.

Rate constants for the reaction of diazodiphenylmethane (DDM) with 4-pyrimidinecarboxylic, 6-hydroxy-4-pyrimidinecarboxylic and 5-hydroxyorotic acids were determined in twelve protic solvents at 30 °C using the well known UV-spectrophotometric method. The second order rate contants for the examined acids were correlated using the appropriate solvent parameters by the equation log k = log k0 + af(e) + bs * + cngH were f(e) is the Kirkwood function of relative permittivity [(e-l)/(2e + 1 )], s * is the Taft polar constant for the alkyl group R in the alcohol ROH, and nyH is themumber of hydrogen atoms in the (-position in the alcohol. The results obtained for the investigated acids were compared with the corresponding results for benzoic, 2- and 3-hydroxybenzoic acids and the influence of the structure of the investigated acids on the reactivity in hydroxylic solvents is discussed. It was also possible to evaluate and distinguish the specific and non-specific solvent effects and their influence on the reaction rate.

The rate constants for the reaction of twenty-two N-(substituted phenylmethylene)- m- and -p-aminobenzoic acids with diazodiphenylmethane were determined in absolute ethanol at 30 °C. The effects of substituents on the reactivity of the investigated compounds were interpreted by correlation of the rate constants with LFER equations. The results of quantum mechanical calculations of the molecular structure together with experimental results gave a better insight into the effects of structure on the transmission of electronic effects of the substituents. New σ constants for substituted benzylideneamino group were calculated.

The rate constants for the reaction of three isomeric pyridine mono-carbocylic acid N-oxides with diazodiphenylmethane were determined at 30 ºC in thirty two protic and aprotic solvents by the well known UV spectrophotometric method. The rate constants are generally higher than for pyridine mono-carboxylic acids in a similar range of solvents, except for picolinic acid N-oxide, and also higher in protic than in aprotic solvents. The determined rate constants were correlated with solvent parameters using the Kamlet-Taft solvatochromic equation bymeans of multiple regression analysis. The sign of the equation coefficients were in agreement with the postulated reaction mechanism. The mode of the influences of the solvent is discussed on the basis of the correlation coefficients, taking into account the specific structures of the pyridine mono-carboxylic acid N-oxides.

A series of N- and N,N-dialkyl-S-alkylthiolcarbamates were synthesized by the rearrangement of N- and N,N-dialkyl-O-alkylthioncarbamates in the presence of diethyl sulfate. The synthesis of some compounds without catalyst was also performed. The compounds were identified by IR, 1H NMR and MS spectroscopic methods. The starting thioncabamates were obtained from the corresponding xanthogenacetates and amines and their structures were also confirmed by IR, 1H NMR and MS data. Some of the thiolcarbamates were characterized for the first time in the literature.

Rate constants for the reaction of diazodiphenylmethane with isomeric pyridine carboxylic acids were determined in chosen protic and aprotic solvents at 30 °C, using the well known UV spectrophotometric method. The values of the rate constants of the investigated acids in protic solvents were higher than those in aprotic solvents. The second order rate constants were correlated with solvent parameters using the Kamlet-Taft solvatochromic equation in the form: logk = logk0 + s¶*+ aα + bβ. The correlation of the obtained kinetic data were performed by means of multiple linear regression analysis taking appropriate solvent parameters. The signs of the equation coefficients were in agreement with the postulated reaction mechanism. The mode of the influence of the solvent on the reaction rate in all the investigated acids are discussed on the basis of the correlation results.

Rate konstants for the reaction of eight 5-substituted orotic acids with diazodiphenylmethane (DDM) in dimethylformamide (DMF) were determined at 30 ºC by the known spectrophotometricmethod. The determined rate constants were correlated with the equations: logk2 = ασ1+βσR+h logk2 = ασ1+βσR+ψν+h to detect the presence and investigate the influence of both electrical and steric substituent effects. The obtained results show that the electrical effect (the localized – field and delocalized – resonance) is predominant and that the steric effect, althought present, is releatively small in this reaction.

The rate constants of 2-substituted nicotinic acids in reaction with diazodiphenylmethane (DDM) in eight alcohols at 30 ºC have been determined. In order to explain the obtained results through solvent effects, the second order reaction rate constants (k) of the examined acids were correlated using the appropriate solvent parameters by the equation: logk=logk0 af(ε) + bσ* + cnγH where f(ε) is the measure of solvent ability as a dielectric to stabilize the separation of opposite charges in the activated complex, σ* is the measure of solvent ability to stabilize proton in the initial state and nγH represents the ability of protic solvents to form hydrogen bond with the negative end of the ion-pair intermediate. These constants were correlated also by using solvatochromic equation of the form logk=logk0 + s¶* + aα + bβ where ¶* is the measure of the solvent polarity, α represents the scale of the solvent hydrogen bond donor acidities (HBD) and β represents the scale of the solvent hydrogen bond acceptor basicities (HBA). The correlations of the kinetic data were carried out by means of multiple linear regression analysis. The results obtained for 2-substituted nicotinic acids were compared with the results for ortho-substituted benzoic acid under the same experimental conditions.