Experimental and Theoretical Studies on Optical Properties of Tetra(Imidazole) of Palladium (II) Phthalocyanine.

In this work, the optical properties of tetra(imidazole) of palladium phthalocyanine (PdPc(Im)4) in solution form and thin films on glass and fluorine-doped tin oxide (FTO) substrates were investigated via the thermal evaporation technique. The optical band gap was evaluated by ultraviolet-visible spectroscopy (UV-Vis). The energy band gap values were determined based on the Tauc graph. In addition, time-dependent density functional theory (TD-DFT) was used to simulate the UV-Vis absorption spectrum of the (PdPc(Im)4) molecule in the Dimethyl Sulfoxide (DMSO) solution phase. A good correlation was found between the DFT results and the experimental optical results. The band gap values between the experimental and DFT-simulated values are presented. The energy band gap of (PdPc(Im)4) obtained from the DFT calculations showed that it can be efficiently regulated. Frontier molecular orbitals and molecular electrostatic potentials were also proposed in this work. The surface study of the layers deposited on FTO was considered by atomic force microscopy (AFM) and scanning electron microscopy (SEM), and the results demonstrated good homogeneity covering the entire surface. The SEM image showed a homogeneous distribution of the grains with some spherical or rod-shaped structures and no agglomeration structures. This work rendered a strategy for regulating the energy band gap and compared the experimental observations obtained with theoretical studies, which provides a fundamental insight into the optical band for optoelectronic and thin-film solar cells.

Hybrid Zinc Phthalocyanine/PVDF-HFP System for Reducing Biofouling in Water Desalination: DFT Theoretical and MolDock Investigations.

Fouling and biofouling remain significant challenges in seawater desalination plants. One practical approach to address these issues is to develop anti-biofouling membranes. Therefore, novel hybrid zinc phthalocyanine/polyvinylidene fluoride-co-hexafluoropropylene (Zn(4-PPOx)4Pc/PVDF-HFP) membranes were prepared by electrospinning to evaluate their properties against biofouling. The hybrid nanofiber membrane was characterized by atomic force microscopy (AFM), attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy, and contact angle measurements. The theoretical calculations of PVDF-HFP, Zn(4-PPOx)4Pc), and Zn(4-PPOx)4Pc/PVDF-HFP nanofibers were performed using a hybrid functional RB3LYP and the 6-31 G (d,p) basis set, employing Gaussian 09. DFT calculations illustrated that the calculated physical and electronic parameters ensured the feasibility of the interaction of PVDF-HFP with Zn(4-PPOx)4Pc via a halogen-hydrogen bond, resulting in a highly stable and remarkably reactive structure. Moreover, molecular electrostatic potential (MEP) maps were drawn to identify the reactive regions of the Zn(4-PPOx)4Pc and PVDF-HFP/Zn(4-PPOx)4Pc nanofibers. Molecular docking analysis revealed that Zn(4-PPOx)4Pc has highest binding affinity (-8.56 kcal/mol) with protein from S. aureus (1N67) mainly with ten amino acids (ASP405, LYS374, GLU446, ASN406, ALA441, TYR372, LYS371, TYR448, LYS374, and ALA442). These findings highlight the promising potential of Zn(4-PPOx) 4Pc/PVDF-HFP nanocomposite membranes in improving the efficiency of water desalination by reducing biofouling and providing antibacterial properties.

Evaluation of environmental and biological monitoring methods for toluene exposure assessment in paint industry.

The aim of this study was to assess the exposure to Toluene in paint industry and to evaluate the environmental and biological monitoring techniques for the assessment of occupational exposure to this aromatic hydrocarbon. In this study, personal active and passive air sampling for toluene measurements, blood and urine sampling respectively for B-Tol and HA or U-Tol analyses for eight workers from two paint and thinner production factories were collected during four successive working days. Correlations were analyzed between biological indicators and environmental toluene exposure levels. The concentration of Toluene measured in air samples ranged from 0.2 to 414.0 ppm (mean = 59.8 ppm), with high variability of atmospheric levels between activities and between days. No significant difference was found between airborne toluene concentrations measured by the two sampling methods. The correlation between air concentrations sampled by the diffusive sampling method and the biomarkers was the best for HA (r = 0.902, p < 0.01), followed by B-Tol (r = 0.820; p < 0.01), o-Cr (r = 0.691; p < 0.01) and U-Tol (r = 0.607; p < 0.05). The correlation was better between air concentrations and urinary metabolites HA and o-Cr for exposure levels higher than 50 ppm (r = 0.931; p < 0.01), and lower than 300 ppm (r = 0.827; p < 0.01), respectively. According to our results, workers in the studied industries are highly exposed to Toluene. Given the high correlation found between toluene concentrations in samples taken on dosimeters and those actively sampled on charcoal tubes, it may be assumed that both sampling methods are valuable. Despite the influencing factors, HA was found to be a reliable biological indicator for the monitoring of occupational exposure to toluene for high exposure levels. However, B-Tol seems to be an interesting alternative, since it is more specific and showed the best correlations with airborne toluene levels.

Synthesis and Characterization of a New Molecularly Imprinted Polymer for Selective Extraction of Mandelic Acid Metabolite from Human Urine as a Biomarker of Environmental and Occupational Exposures to Styrene.

4-Vinylpyridine molecularly imprinted polymer (4-VPMIP) microparticles for mandelic acid (MA) metabolite as a major biomarker of exposure to styrene (S) were synthesized by bulk polymerization with a noncovalent approach. A common mole ratio of 1:4:20 (i.e., metabolite template: functional monomer: cross-linking agent, respectively) was applied to allow the selective solid-phase extraction of MA in a urine sample followed by high-performance liquid chromatography-diode array detection (HPLC-DAD). In this research, the 4-VPMIP components were carefully selected: MA was used as a template (T), 4-Vinylpyridine (4-VP) as a functional monomer (FM), ethylene glycol dimethacrylate (EGDMA) as a cross-linker (XL), and azobisisobutyronitrile (AIBN) as an initiator (I) and acetonitrile (ACN) as a porogenic solvent. Non-imprinted polymer (NIP) which serves as a "control" was also synthesized simultaneously under the same condition without the addition of MA molecules. Fourier transform infrared (FT-IR) spectroscopy and scanning electron microscopy (SEM) were used to characterize the imprinted and nonimprinted polymer to explain the structural and morphological characteristics of the 4-VPMIP and surface NIP. The results obtained from SEM depicted that the polymers were irregularly shaped microparticles. Moreover, MIPs surfaces had cavities and were rougher than NIP. In addition, all particle sizes were less than 40 µm in diameter. The IR spectra of 4-VPMIPs before washing MA were a little different from NIP, while 4-VPMIP after elution had a spectrum that was almost identical to the NIP spectrum. The adsorption kinetics, isotherms, competitive adsorption, and reusability of 4-VPMIP were investigated. 4-VPMIP showed good recognition selectivity as well as enrichment and separation abilities for MA in the extract of human urine with satisfactory recoveries. The results obtained in this research imply that 4-VPMIP might be used as a sorbent for MA solid-phase extraction (MISPE), for the exclusive extraction of MA in human urine.

Synthesis of a New Molecularly Imprinted Polymer and Optimisation of Phenylglyoxylic Acid Extraction from Human Urine Samples Using a Central Composite Design within the Response Surface Methodology.

Styrene, a chemical widely used in various industries, undergoes metabolic breakdown in the human body, resulting in the production of phenylglyoxylic acid (PGA). A novel molecularly imprinted polymer (MIP) was synthesised for selective extraction and enrichment of PGA in urine samples prior to high-performance liquid chromatography. The MIP employed in this research was a 4-vinylpyridine molecularly imprinted polymer (4-VPMIP) prepared via mass polymerisation using a noncovalent method. The structural and morphological characteristics of the molecularly imprinted polymers (MIPs) and non-imprinted polymers (NIPs) were evaluated using Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM). The efficiency of the molecularly imprinted solid-phase extraction (MISPE) process was optimised by investigating critical variables such as sample pH, sorbent mass, sample flow rate, and volume of the elution solvent. A central composite design (CCD) within the response surface methodology was utilised to develop separate models for the adsorption and desorption steps. Analysis of variance (ANOVA) confirmed the excellent fit of the experimental data to the proposed response models. Under the optimised conditions, the molecularly imprinted polymers exhibited a higher degree of selectivity and affinity for PGA, with a relative selectivity coefficient (α) of 2.79 against hippuric acid. The limits of detection (LOD) and quantification (LOQ) for PGA were determined to be 0.5 mg/L and 1.6 mg/L, respectively. The recoveries of PGA ranged from 97.32% to 99.06%, with a relative standard deviation (RSD) lower than 4.6%. Furthermore, MIP(4VP)SPE demonstrated the potential for recycling up to three times without significant loss in analyte recovery.

Design of a New Phthalocyanine-Based Ion-Imprinted Polymer for Selective Lithium Recovery from Desalination Plant Reverse Osmosis Waste.

In this study, a novel technique is introduced that involves the combination of an ion-imprinted polymer and solid-phase extraction to selectively adsorb lithium ions from reverse osmosis brine. In the process of synthesizing ion-imprinted polymers, phthalocyanine acrylate acted as the functional monomer responsible for lithium chelation. The structural and morphological characteristics of the molecularly imprinted polymers and non-imprinted polymers were assessed using Fourier transform infrared spectroscopy and scanning electron microscopy. The adsorption data for Li on an ion-imprinted polymer showed an excellent fit to the Langmuir isotherm, with a maximum adsorption capacity (Qm) of 3.2 mg·g-1. Comprehensive chemical analyses revealed a significant Li concentration with a higher value of 45.36 mg/L. Through the implementation of a central composite design approach, the adsorption and desorption procedures were systematically optimized by varying the pH, temperature, sorbent mass, and elution volume. This systematic approach allowed the identification of the most efficient operating conditions for extracting lithium from seawater reverse osmosis brine using ion-imprinted polymer-solid-phase extraction. The optimum operating conditions for the highest efficiency of adsorbing Li+ were determined to be a pH of 8.49 and a temperature of 45.5 °C. The efficiency of ion-imprinted polymer regeneration was evaluated through a cycle of the adsorption-desorption process, which resulted in Li recoveries of up to 80%. The recovery of Li from the spiked brine sample obtained from the desalination plant reverse osmosis waste through the ion-imprinted polymer ranged from 62.8% to 71.53%.

Thermomechanical Autovaporization (MFA) as a Deodorization Process of Palm Oil.

Throughout the vegetable oil industry, there is a focus on eradicating the volatile molecules affecting the aroma or taste of the crude oil, whether it is natural or derived from the extraction process. Refining aims to reduce these compounds to a level acceptable to the consumer. In addition, the famous conventional operation of deodorization calls for high levels of temperature depending on the boiling point used to remove the atmospheric pressure of each molecule. The process implies a vacuum level between 10 to 80 kPa absolute pressure, a temperature generally between 190 and 240 °C, and a duration of 2 to 3 h. These conditions necessarily (inevitably) lead to a decrease in the quality of refined oil. Recently, the application of the Multi-Flash Autovaporization "MFA" operation has shown the possibility of eradicating volatile molecules while adopting relatively low temperature and time levels. Despite the high boiling temperature of the volatile organic compounds (VOC), MFA leads to good efficiency in reducing VOCs and preserving oil quality. The main odorant compounds in the crude palm oil were E-2-Hexenal, heptanal, octanal, nonanal, and decanal. Specific literature can indicate precise boiling temperatures under atmospheric pressure. In addition, many experimental studies have explained the evolution of each molecule and shown how they depend on the operating parameters (inlet oil pressure from 200 to 450 kPa and from 5 and 30 s time of each cycle, and the number of cycles up to 7), and how the empirical mathematical models describe the MFA deodorization, estimate the efficiency of the whole process, and optimize the operating parameters. In this research, the thermodynamic data of absolute pressure volatility versus temperature was used to better identify the removal rate (up to around 87%) implied by an abrupt pressure drop to a vacuum of 5 kPa for p = 450 kPa, t = 25 s/cycle, and the number of cycles (C = 6). The safeguarding of the fatty acid profile illustrated the maintenance of the oil quality.

Impedance Spectroscopy and Dielectric Relaxation of Imidazole-Substituted Palladium(II) Phthalocyanine (ImPdPc) for Organic Solar Cells.

In this study, we investigated the potential of palladium tetrakis (imidazole) phthalocyanine (PdPc(Imz)4) for use as an organic semiconductor for improving the photovoltaic performance. In order to get more information about the prevailing model of the conduction mechanism (correlated barrier hopping (CBH)) for PdPc(Imz)4, electrical impedance measurements were performed at different temperatures and the obtained data were simulated by the Kohlraush Williams Watt (KWW) approach. Theoretical studies (density functional theory (DFT)) were performed and molecular electrostatic potential (MEP) maps were also extracted to understand the relationship between the molecular structures and the molecular electronic structure of PdPc(Imz)4 and its semiconductor properties. Furthermore, studies on the AC electrical process as a function of temperature highlighted a hopping charge transport according to an equivalent electrical circuit composed of a parallel constant-phase element (CPE), capacitance in the grain boundary layer (C g), and resistance of the grain boundary (R g). To improve interpretation of the results, an in-depth analysis of the behavior of the electric transport was conducted. As a result, the correlated barrier hopping (CBH) conduction mechanism was shown to be the most suitable predominant conduction mechanism.

Inhalant abuse detection and evaluation in young Tunisians.

Occupational exposure biological monitoring techniques were applied for the diagnosis of inhalation abuse and for the evaluation of the levels of exposure to benzene, toluene, ethylbenzene, xylenes, and n-hexane, in 44 Tunisian adolescents and children suspected for volatile substance addiction. Urinary trans,trans-muconic acid, hippuric acid (HA), mandelic acid, and methylhippuric acids determinations were performed by high performance liquid chromatography with a photodiode array detector, and urinary o-cresol (o-Cr) and 2,5-hexanedione (HD) were extracted simultaneously and measured using gas chromatography with a flame ionization detector. Given the high linearity ranges, HD and o-Cr occupational exposure monitoring techniques could be applied without modification. However, urinary sample dilution was necessary before HA analysis. Concentrations were compared with the maxima of normal values (MNVs) in the general population and to the biological exposure indices (BEIs) used in occupational toxicology. Values as high as 6610-fold the MNV and 68 times the BEI were registered. The subjects showed high exposure to toluene and hexane. Measured metabolites HA and/or o-Cr and HD enabled the easy detection and evaluation of exposure levels. The problem of inhalant abuse should be given more attention and treated through an effective prevention strategy.

Benzene exposure monitoring of Tunisian workers.

To monitor benzene exposure and to check reliability of urinary trans,trans-Muconic Acid (t,t-MA) as a bio-marker of benzene exposure in local conditions, a study was conducted on 30 Tunisian exposed workers (20 tanker fillers and 10 filling station attendants). The analyses were carried out on environmental air and urinary t,t-MA before (t,t-MAA) and at the end of work shift (t,t-MAB). 20 nonoccupationally exposed subjects were also investigated. The average value of environmental benzene concentration was 0.17 ppm. The differences between t,t-MAA and t,t-MAB concentrations and between t,t-MAB and t,t-MA measured in controls (t,t-MAC) were both significant (p < 0.001). Benzene air concentrations were well correlated with t,t-MAB: R = 0.76. In the nonexposed group, average t,t-MA concentrations is significantly higher among smokers than nonsmokers (P < 0.02). Analysis of urinary t,t-MA offers a relatively simple and suitable method for benzene exposure monitoring.