Spectroscopic and Structural Study of a New Conducting Pyrazolium Salt.

The increase in conductivity with temperature in 1H-pyrazol-2-ium 2,6-dicarboxybenzoate monohydrate was analyzed, and the influence of the mobility of the water was discussed in this study. The electric properties of the salt were studied using the impedance spectroscopy method. WB97XD/6-311++G(d,p) calculations were performed, and the quantum theory of atoms in molecules (QTAiM) approach and the Hirshfeld surface method were applied to analyze the hydrogen bond interaction. It was found that temperature influences the spectroscopic properties of pyrazolium salt, particularly the carbonyl and hydroxyl frequencies. The influence of water molecules, connected by three-center hydrogen bonds with co-planar tetrameters, on the formation of structural defects is also discussed in this report.

Synthesis and characterization of optically active magnetic PAI/Fe3O4 nanocomposites.

This work presents the preparation and characterization of hybrid organic-inorganic optically active poly(amide-imide)/nano-Fe3O4 composites with different amount of modified Fe3O4 nanoparticles as new nanocomposites by ultrasonic irradiation and characterized by Fourier transform infrared spectra, X-ray diffraction, scanning electron microscopy (SEM), thermogravimetric analysis and vibrating sample magnetometry. The surface of Fe3O4 nanoparticles was modified with 3-aminopropyltriethoxyl silane because of the homogeneous distribution of nano-Fe3O4 in polymer matrix, which the SEM results confirmed that the Fe3O4 nanoparticles were dispersed uniformly in polymer matrix. Furthermore, as compared with pure polymer, thermogravimetric analysis data indicated an improvement of thermal stability of nanocomposites.

Chemically and thermally stable silica nanowires with a ß-sheet peptide core for bionanotechnology.

BACKGROUND: A series of amyloidogenic peptides based on the sequence KFFEAAAKKFFE template the silica precursor, tetraethyl orthosilicate to form silica-nanowires containing a cross-ß peptide core. RESULTS: Investigation of the stability of these fibres reveals that the silica layers protect the silica-nanowires allowing them to maintain their shape and physical and chemical properties after incubation with organic solvents such as 2-propanol, ethanol, and acetonitrile, as well as in a strong acidic solution at pH 1.5. Furthermore, these nanowires were thermally stable in an aqueous solution when heated up to 70 °C, and upon autoclaving. They also preserved their conformation following incubation up to 4 weeks under these harsh conditions, and showed exceptionally high physical stability up to 1000 °C after ageing for 12 months. We show that they maintain their ß-sheet peptide core even after harsh treatment by confirming the ß-sheet content using Fourier transform infrared spectra. The silica nanowires show significantly higher chemical and thermal stability compared to the unsiliconised fibrils. CONCLUSIONS: The notable chemical and thermal stability of these silica nanowires points to their potential for use in microelectromechanics processes or fabrication for nanotechnological devices.

A comparative study of occurrence and fate of endocrine disruptors: diethyl phthalate and dibutyl phthalate in ASP- and SBR-based wastewater treatment plants.

Phthalates are endocrine-disrupting chemicals which affect endocrine system by bio-accumulation in aquatic organisms and produce adverse health effects in aquatic organisms as well as human beings, when come in contact. Present study focuses on occurrence and removal of two phthalates: diethylphthalate (DEP) and dibutylphthalate (DBP) in two full-scale wastewater treatment plants (WWTPs) i.e. sewage treatment plants (STPs) based on well-adopted technologies, activated sludge process (ASP) and sequencing batch reactor (SBR).Gas chromatography-mass spectrometry (GC-MS) analysis was performed for both wastewater and sludge sample for determination and identification of the concentration of these compounds in both STPs by monitoring the STPs for 9 months. It was observed that the concentration of DEP was less than DBP in the influent of ASP and SBR. Average concentrations of DEP and DBP in sludge sample of ASP were found to be 2.15 and 2.08 ng/g, whereas in SBR plant, these values were observed as 1.71 and 2.01 ng/g, respectively. Concerning the removal efficiency of DEP, SBR and ASP plants were found effective with removal efficiency of 91.51 and 91.03 %, respectively. However, in the case of DBP, SBR showed lower removal efficiency (85.42 %) as compared to ASP (92.67 %). Comparative study of both plants proposed that in ASP plant, DBP reduction was higher than the SBR. Fourier transformation infrared (FTIR) analysis also confirmed the same result of sludge analysis for both STPs. Sludge disposal studied with scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX) and thermo-gravimetric analysis (TGA) techniques confirmed that sludge of both STPs have high calorific value and can be used as fuel to make fuel-briquettes and bottom ash to make firebricks.

Crystal structure of the sodium salt of mesotrione: a triketone herbicide.

The crystal structure of the sodium salt of mesotrione, namely, catena-poly[[sodium-µ3-2-[(4-methane-sulfonyl-2-nitro-phen-yl)carbon-yl]-3-oxo-cyclo-hex-1-en-1-olato] ethanol monosolvate], {[Na(C14H12NO7S)]C2H5OH}n, is described. The X-ray structural analysis results reveal that the coordination sphere is established by two chelating O atoms, the O atom of the coordinated ethanol mol-ecule, and an O atom from the methyl-sulfonyl group of a neighboring mol-ecule. Simultaneously, an O atom of the cyclo-hexane fragment serves as a bridge to a neighboring sodium ion, forming a flat Na-O-Na-O quadrangle, thereby forming a mono-periodic polymer. The structure displays O-H⋯O hydrogen bonds and C-H⋯O short contacts. Thermogravimetric analysis (TGA) data indicate that the sodium salt of mesotrione decomposes in four stages.

Machine Learning Analysis of Enhanced Biodegradable Phoenix dactylifera L./HDPE Composite Thermograms.

Worldwide, environmental groups and policymakers are focusing on waste recycling to create economic value and on the decomposition of waste by leveraging on scarce resources. This work, therefore, explores the thermal decomposition of enhanced biodegradable polymer matrices made from a mixture of discarded Phoenix dactylifera L./high-density polyethylene (PD/HDPE) using the machine learning analysis of experimental data. The experimental results of these samples were obtained via thermogravimetric (TGA) analysis under an oxidation-free environment, with heating rates of 10, 20, and 40 °C·min-1 and a degradation temperature range from 25 to 600 °C. The TGA analyses revealed the continued dependence of the actual percentage weight loss by these materials as a test function of the degradation temperature, shifting thermograms to temperature maxima consistent with increasing heating rates. Although high-density polyethylene (HDPE) materials were found to be thermally more stable than Phoenix dactylifera L. (PD) materials, PD/HDPE composite materials contained a significant amount of residual ash. Using a machine learning deep neural network approach for this process, significantly improved learning algorithms have been developed, which reduces the overall cost function (residual error) to almost zero (0.025) after just over a million iterations (epochs) and provides predictions that overlap with the experimental results (R2~1). Learning algorithms, along with optimized synaptic weights and biases, were employed to predict the behaviour of PD materials based on experimental thermograms conducted at higher degradation temperatures, typically ranging between 600 and 1000 °C. Predicted data using the enhanced learning algorithms completely overlapped the experiments (R2~1) for these higher degradation temperatures with near unity correlation if the decomposition of the materials continued until the residue was attained. With this approach, it is possible to predict and optimize the thermal characteristics of PD and HDPE with greater efficiency, which reduces the need for multiple design iterations and experimentation.

Mechano Chemical Compatibilization of Polyethylene with Graphite by Means of a Suitable Ester.

An effective non-covalent compatibilization method for graphite and low-density polyethylene is reported. To obtain this result, pyren-1-yl-stearate (P1S) was synthesized, characterized and mixed with graphite to provide a better dispersion in polyethylene matrix. The P1S improves the dispersion of carbon filler in polyethylene through non-covalent compatibilization: the pyrenyl group gives π-π stacking interactions with graphite and the stearyl chain provides van der Waals interaction with the polymer chain (specifically London dispersion forces). In this study, different P1S/graphite fillers were prepared with a ratio by weight of 90/10 and 50/50, respectively, by using manual and ball-milling mixing. Their stability, interaction and morphology were evaluated through TGA, RX, and SEM. Thermogravimetric analyses showed that ball-milling mixing is more effective than manual mixing in promoting π-π stacking interactions of molecules such as P1S ester containing an alkyl chain and aromatic rings. The role of ball milling is confirmed by X-ray diffraction measurements since it was possible to observe both exfoliation and intercalation phenomena when this technique was used to mix the P1S ester with graphite. SEM analyses of polyethylene containing 1% of the carbon fillers again highlighted the importance of ball milling to promote the interaction of the ester with graphite and, simultaneously, the importance of the alkyl chain in order to achieve polyethylene-graphite compatibilization.

Characterization of solid biomass briquette biofuel from the wastes of Senna auriculata and Ricinus communis using Tapioca starch for sustainable environment.

Biomass energy contributes nearly 14% of the total global energy. Therefore, biomass briquettes can be effectively considered an alternate source of fossil fuels. The present study aims at utilizing Senna auriculata and Ricinus communis waste generated locally for the production of biomass briquettes with 10% of tapioca starch as binder. The biomass wastes are blended at various proportions such as 0:100 (S1), 25:75 (S2), 50:50 (S3), 75:25 (S4) and 100:0 (S5) respectively, and the concentration of binder was maintained to be constant. The characterization of the prepared biomass briquettes includes the analysis of physical characteristics, proximate analysis, elemental analysis, SEM analysis, thermogravimetric analysis, differential scanning calorimetric analysis and XRD analysis. The results of the proximate analysis have revealed that the biomass briquettes possess lower percentage in terms of moisture content, ash content, sensible fixed carbon and high percentage of volatile matter content. Energy dispersive X-ray analysis has shown that the carbon and oxygen are the major elements for all the biomass briquettes. SEM analysis has revealed that the surface of the biomass briquettes is identified with irregular surface, lumps, cavities and few deposits of carbon particles. Thermogravimetric analysis and DSC analysis have reconfirmed the spontaneous burning characteristics of biomass briquettes. XRD analysis has proved that the bonding between each element present in the biomass briquettes is either monoclinic, tetragonal, orthorhombic or anorthic.

Thermal Stability and Non-Isothermal Kinetic Analysis of Ethylene-Propylene-Diene Rubber Composite.

The purpose of this study was to investigate the thermal stability and the decomposition kinetics of ethylene-propylene-diene monomer (EPDM) composite samples loaded with and without lead powder (50, 100, and 200 phr lead) using thermogravimetric analysis (TGA). TGA was carried out at different heating rates (5, 10, 20, and 30 °C/min) under inert conditions in the temperature range of 50-650 °C. Lead addition did not significantly change the onset temperature or peak position corresponding to the maximum decomposition rate of the first derivative of the TGA curve (DTGA) (onset at about 455 °C and Tm at about 475 °C). Peak separation for the DTGA curves indicated that the main decomposition region for EPDM, the host rubber, overlapped the main decomposition region for volatile components. The decomposition activation energy (Ea) and pre-exponent factor (A) were estimated using the Friedman (FM), Kissinger-Akahira-Sunose (KAS), and Flynn-Wall-Ozawa (FWO) iso-conversional methods. Average activation energy values of around 231, 230, and 223 kJ/mol were obtained for the EPDM host composite using the FM, FWO, and KAS methods, respectively. For a sample loaded with 100 phr lead, the average activation energy values obtained via the same three methods were 150, 159, and 155 kJ/mole, respectively. The results obtained from the three methods were compared with results obtained using the Kissinger and Augis-Bennett/Boswell methods, and strong convergence was found among the results of the five methods. A significant change in the entropy of the sample was detected with the addition of lead powder. For the KAS method, the change in entropy, ΔS, was -3.7 for EPDM host rubber and -90 for a sample loaded with 100 phr lead, α = 0.5.

Insights on kinetic triplets and thermodynamic analysis of Delonix regia biomass pyrolysis.

The aim of this work was to study the pyrolysis of Delonix regia biomass with non-isothermal thermogravimetric experiments. The targeted objective was to investigate kinetic triplets and thermodynamic parameters. Five iso-conversional methods, namely Differential Friedman, Kissinger-Akahira-Sunose, Ozawa-Flynn-Wall, Starink, and Distributed Activation Energy, have been considered. In the adopted heating rates of 5-55 °C min-1, the average activation energy and pre-exponential factor varied in the range 202.34-205.89 kJ mol-1 and 4.98 × 1017 - 2.04 × 1020 s-1 respectively. Corresponding average enthalpy and Gibbs free energy varied from 196.84 to 200.87 kJ mol-1 and from 182.64 to 206.41 kJ mol-1 respectively. Pyrolysis mechanism have been confirmed by Avrami-Erofeyev (A4), power-law (P2 and P4) and reaction (F1, F2, and ≥ F5) according to Criado's master plots.

A comparative study on physicochemical properties, pyrolytic behaviour and kinetic parameters of environmentally harmful aquatic weeds for sustainable shellfish aquaculture.

Aquatic weeds pose hazards to aquatic ecosystems and particularly the aquatic environment in shellfish aquaculture due to its excessive growth covering entire freshwater bodies, leading to environmental pollution particularly eutrophication intensification, water quality depletion and aquatic organism fatality. In this study, pyrolysis of six aquatic weed types (wild and cultured species of Salvinia sp., Lemna sp. and Spirodella sp.) were investigated to evaluate its potential to reduce and convert the weeds into value-added chemicals. The aquatic weeds demonstrated high fixed carbon (8.7-47.3 wt%), volatile matter content (39.0-76.9 wt%), H/C ratio (1.5-2.0) and higher heating value (6.6-18.8 MJ/kg), representing desirable physicochemical properties for conversion into biofuels. Kinetic analysis via Coats-Redfern integral method obtained different orders for chemical reaction mechanisms (n = 1, 1.5, 2, 3), activation energy (55.94-209.41 kJ/mol) and pre-exponential factor (4.08 × 104-4.20 × 1017 s-1) at different reaction zones (zone 1: 150-268 °C, zone 2: 268-409 °C, zone 3: 409-600 °C). The results provide useful information for design and optimization of the pyrolysis reactor and establishment of the process condition to dispose this environmentally harmful species.

Fabrication of Co3O4 from Cobalt/2,6-Napthalenedicarboxylic Acid Metal-Organic Framework as Electrode for Supercapacitor Application.

In this study, cobalt-based metal-organic framework (MOF) powder was prepared via the solvothermal method using 2,6-naphthalenedicarboxylic acid (NDC) as the organic linker and N,N-dimethylformamide (DMF) as the solvent. The thermal decomposition of the pristine cobalt-based MOF sample (CN-R) was identified using a thermogravimetric examination (TGA). The morphology and structure of the MOFs were modified during the pyrolysis process at three different temperatures: 300, 400, and 500 °C, which labeled as CN-300, CN-400, and CN-500, respectively. The results were evidenced via field-emission scanning electron microscopy (FESEM), energy dispersive X-ray spectroscopy (EDX) and X-ray diffraction (XRD). The crystallite size of all samples was calculated using Scherrer's equation. The smallest crystallite size of 7.77 nm was calculated for the CN-300 sample. Fourier transform infrared spectroscopy (FTIR) spectra were acquired for all the samples. The graphical study of the cyclic voltammogram (CV) gave the reduction and oxidation peaks. The charge transfer resistance and ionic conductivity were studied using electrical impedance spectroscopy (EIS). The galvanostatic charge-discharge (GCD) responses of all samples were analyzed. The relatively high specific capacitance of 229 F g-1 at 0.5 A g-1 was achieved in the sample CN-300, whereby 110% of capacitance was retained after 5000 cycles. These findings highlighted the durability of the electrode materials at high current densities over a long cycle.

Evaluation of combustion properties and pollutant emission characteristics of blends of sewage sludge and biomass.

The combustion and emission characteristics of sludge, biomass (rice husk, peanut husk, pine sawdust) and their blends were studied by non-isothermal thermogravimetry, tube oven method and SEM. The results showed that the combustion process of sludge, biomass and their blends could be divided into three stages: the evaporation of water, the release and combustion of volatile, combustion of char. Combustion characteristics of 80% biomass +20% sludge were improved compared with the theoretical value. NOx and SO2 emission of 80% biomass +20% sludge was lower than that of sludge combustion. There was synergistic effect between sludge/biomass combustion. Comparing combustion and emission characteristics comprehensively, the mixed fuels of 80% biomass +20% sludge could promote combustion and reduce emissions, which was a better method to treat municipal sludge.

Influence of Fluorine Substitution on the Optical, Thermal, Electrochemical and Structural Properties of Carbazole-Benzothiadiazole Dicarboxylic Imide Alternate Copolymers.

In this work four novel donor-acceptor copolymers, PCDTBTDI-DMO, PCDTBTDI-8, P2F-CDTBTDI-DMO and P2F-CDTBTDI-8, were designed and synthesised via Suzuki polymerisation. The first two copolymers consist of 2,7-carbazole flanked by thienyl moieties as the electron donor unit and benzothiadiazole dicarboxylic imide (BTDI) as electron acceptor units. In the structures of P2F-CDTBTDI-DMO and P2F-CDTBTDI-8 copolymers, two fluorine atoms were incorporated at 3,6-positions of 2,7-carbazole to investigate the impact of fluorine upon the optoelectronic, structural and thermal properties of the resulting polymers. P2F-CDTBTDI-8 possesses the highest number average molecular weight (Mn = 24,200 g mol-1) among all the polymers synthesised. PCDTBTDI-DMO and PCDTBTDI-8 show identical optical band gaps of 1.76 eV. However, the optical band gaps of fluorinated copolymers are slightly higher than non-fluorinated counterparts. All polymers have deep-lying highest occupied molecular orbital (HOMO) levels. Changing the alkyl chain substituents on BTDI moieties from linear n-octyl to branched 3,7-dimethyloctyl groups as well as substituting the two hydrogen atoms at 3,6-positions of carbazole unit by fluorine atoms has negligible impact on the HOMO levels of the polymers. Similarly, the lowest unoccupied molecular orbital (LUMO) energy levels are almost comparable for all polymers. Thermogravimetric analysis (TGA) has shown that all polymers have good thermal stability and also confirmed that the fluorinated copolymers have higher thermal stability relative to those non-fluorinated analogues. Powder X-ray diffraction (XRD) studies proved that all polymers have an amorphous nature in the solid state.

Optimization of ultrasound-assisted solvent extraction (UASE) based on oil yield, antioxidant activity and evaluation of fatty acid composition and thermal stability of Coriandrum sativum L. seed oil.

Ultrasound is one of emerging technique's which is being investigated extremely on food applications and extraction process. In this study, ultrasound-assisted solvent extraction was employed to extract vegetable oil from coriander (Coriandrum sativum L.) seeds. A response surface model was applied to determine the best condition of extraction concerning the independent factors (COY % and DPPH %). In addition, ultrasound variables were the sample solvent ratio, amplitude level, temperature and time. The best condition of extraction was obtained for sample solvent ratio of 1:13 (g/mL), amplitude level of 82 (%), temperature of 45 (°C) and extraction time of 9 (min), being the maximum point of oil yield and antioxidant activity (30.74-72.05%), respectively. Fatty acid profile of oil has been shown as a rich source of petroselinic acid (C18:1)-12, making up 76% of all fatty acids. TGA analyses revealed that 82% (by weight) of oil is thermally stable up to 224 °C.

Characterization of alkali treated and untreated new cellulosic fiber from Saharan aloe vera cactus leaves.

The aim of this study is to examine the use of new natural fibers, which are extracted from the Saharan aloe vera cactus plant leaves as reinforcement in polymer composites. The physicochemical, mechanical and thermal properties of the Saharan Aloe Vera Cactus Leaves (SACL) fibers are investigated, through the effect of alkali treatment. The contents of α-cellulose, hemicellulose, wax and moisture present in SACL fibers were characterized by standard test methods The mechanical properties of SACL fibers were measured through single fiber tensile test. The interfacial strength between the fiber and matrix was estimated by the fiber pull-out test. These results ensure that the chemical and mechanical properties of the fibers are improved after the alkali treatment. FT-IR spectroscopic analysis confirms that the alkali treatment process has removed certain amount of amorphous materials from the fibers. XRD analysis results show that the alkali treatment has enhanced the Crystallinity Index and Crystalline Size of the fibers. Thermal behavior of the fibers was analyzed by using TGA. The thermal stability and the thermal degradation temperature increases after the alkali treatment of fibers. The morphologies of fibers were analyzed by SEM and prove that the fiber surfaces become rough after alkali treatment.

Poly[(µ5-3-carboxybenzene-1,2-dicarboxylato)lead(II)]: a helical lead(II) coordination polymer.

In the title polymer, [Pb(C9H4O6)]n, the asymmetric unit contains a monomer of a Pb(II) cation with a doubly deprotonated 3-carboxybenzene-1,2-dicarboxylate dianion (1,2,3-Hbtc(2-)). Each Pb(II) centre is seven-coordinated by seven O atoms of bridging carboxy/carboxylate groups from five 1,2,3-Hbtc(2-) ligands, forming a distorted pentagonal bipyramid. The Pb(II) cations are bridged by 1,2,3-Hbtc(2-) anions, yielding two-dimensional chiral layers. The layers are stacked above each other to generate a three-dimensional supramolecular architecture via a combination of C-H···O interactions. The thermogravimetric and optical properties are also reported.