Design, characterization and implementation of cost-effective sodium alginate/water hyacinth microspheres for remediation of lead and cadmium from wastewater.

The aquatic plant water hyacinth was dried then cross-linked with sodium alginate to produce ionic cross-linked microspheres. The mechanism of controlling cadmium (Cd) and lead (Pb) in wastewater was tested by DFT at B3LYP level using LANL2DZ basis set. Modeling results indicated that the hydrated metals could interact with sodium alginate (SA)/water hyacinth (WH) microspheres through hydrogen bonding. Adsorption energies showed comparable results while total dipole moment and HOMO/LUMO band gap energy showed slight selectivity towards the remediation of Pb. FTIR spectra of cross-linked microspheres indicated that WH is forming a composite with SA to change its structure into a microsphere to remove Cd and Pb from water. Raman mapping revealed that the active sites along the surface of the microspheres enable for possible adsorption of metals through its surface. This finding is supported by molecular electrostatic potential and optical confocal microscopy. Atomic absorption spectroscopy results confirmed that the microspheres are more selective for Pb than Cd. It could be concluded that WH cross-linked with SA showed the potential to remove heavy metals through its unique active surface as confirmed by both molecular modeling and experimental findings.

Molecular modeling analysis for functionalized graphene/sodium alginate composite.

This study examined the functionalization of graphene with easily ionizable elements, such as lithium, and subsequently its interaction with the biopolymer sodium alginate (SA), to highlight its potential for biomedical applications. Utilizing Density Functional Theory (DFT), the research comprehensively investigated the structural, electronic, and spectroscopic properties of these graphene-based composites. The electronic properties of functionalized graphene were investigated using DFT at the B3LYP/6-31G(d,p) level. Among the various configurations studied, graphene exhibited weak interaction with two lithium atoms, displaying the highest reactivity in terms of total dipole moment (TDM) at 5.967 Debye and a HOMO/LUMO energy gap (ΔE) of 0.748 eV. Electrostatic potential mapping revealed that graphene when enhanced with lithium and three units of SA, exhibited an augmented potential density on its surface, a finding corroborated by other investigated physical properties. Notably, the configuration of graphene/3SA/Li, with weak interaction occurring at two side carbons, demonstrated the highest reactivity with a TDM of 15.509 Debye and ΔE of 0.280 eV. Additionally, a shift in the spectral characteristics of graphene towards lower wavenumbers was observed as lithium and SA interacted with the graphene substrate. The PDOS plot for Graphene/3SA/Li, showed the highest contribution in the HOMO orbitals was equally from lithium, sodium, hydrogen, and oxygen, while the lowest contribution was from carbon. This computational analysis provides comprehensive insights into the functionalized graphene systems, aiding in their further development and optimization for practical biomedical use.

Two-Dimensional MXene as a Promising Adsorbent for Trihalomethanes Removal: A Density-Functional Theory Study.

This groundbreaking research delves into the intricate molecular interactions between MXene and trihalomethanes (THs) through a comprehensive theoretical study employing density-functional theory (DFT). Trihalomethanes are common carcinogenic chlorination byproducts found in water sanitation systems. This study focuses on a pristine MXene [Mn+1·Xn] monolayer and its various terminal [Tx] functional groups [Mn+1·XnTx], strategically placed on the surface for enhanced performance. Our investigation involves a detailed analysis of the adsorption energies of THs on different MXene types, with the MXene-Cl layer emerging as the most compatible variant. This specific MXene-Cl layer exhibits remarkable properties, including a total dipole moment (TDM) of 12.443 Debye and a bandgap of 0.570 eV, achieved through meticulous geometry optimization and computational techniques. Notably, THs such as trichloromethane (CHCl3), bromide-chloromethane (CHBrCl2), and dibromochloromethane (CHBr2Cl) demonstrate the highest TDM values, indicating substantial changes in electronic and optical parameters, with TDM values of 16.363, 15.998, and 16.017 Debye, respectively. These findings highlight the potential of the MXene-Cl layer as an effective adsorbent and detector for CHF3, CHClF2, CHCl3, CHBrCl2, and CHBr2Cl. Additionally, we observe a proportional increase in the TDM and bandgap energy, indicative of conductivity, for various termination atom combinations, such as Mxene-O-OH, Mxene-O-F, Mxene-O-Cl, Mxene-OH-F, Mxene-F-Cl, and Mxene-OH-Cl, with bandgap energies measured at 0.734, 0.940, 1.120, 0.835, and 0.927 eV, respectively. Utilizing DFT, we elucidate the adsorption energies of THs on different MXene surfaces. Our results conclusively demonstrate the significant influence of the termination atom nature and quantity on MXene's primitive TDM value. This research contributes to our understanding of MXene-THs interactions, offering promising avenues for the development of efficient adsorbents and detectors for THs. Ultimately, these advancements hold the potential to revolutionize water sanitation practices and enhance environmental safety.

Effect of alkali metals on physical and spectroscopic properties of cellulose.

A 3-unit cellulose model molecule was built and optimized using DFT B3LYP/6-31G(d,p). The electronic properties of the optimized structure of cellulose were investigated in terms of total dipole moment (TDM), HOMO-LUMO band gap (ΔE), and molecular electrostatic potential (MESP). Cellulose demonstrated a TDM of 9.106 Debye and ΔE of 7.647 eV. The hydrogen atom of the hydroxyl group of the CH2OH group of each cellulose unit was replaced by an alkali metal atom (X) such that the 3-unit cellulose once had 1X atom, then 2X, then 3X atoms, where X = Li, Na or K, both without and with 2, 4 and 6 water molecules (W), respectively, to study also the effect of hydration. Without hydration, the values of TDM decreased for all of the proposed interaction, but increased with hydration, while ΔE decreased in all interactions, confirming that interaction cellulose-alkali metal interaction, especially with hydration, resulted in more reactive structures. Mapping of HOMO-LUMO and MESP indicated significant change in the electron density distribution around cellulose under the effect of interaction with the alkali metals, both with and without hydration. The plots of projected density of states also clearly demonstrated the contribution of each alkali metal as well as water in the molecular orbitals, reflecting their effect on the electronic properties of cellulose and cellulose-alkali metals composites. The theoretical calculations were experimentally verified using FTIR and FT-Raman spectroscopy.

UV filters and high refractive index materials based on carboxymethyl cellulose sodium and CuO@ZnO core/shell nanoparticles.

Nanoparticles have substantially contributed to the field of skincare products with ultraviolet (UV) filters to preserve human skin from sun damage. Thus, the current study aims to develop new polymer nanocomposites for the efficient block of UV light that results from the stratospheric ozone layer loss. Co-precipitation method was used to successfully synthesis CuO@ZnO core/shell NPs with a well-crystalline monoclinic CuO core and wurzite ZnO shell. Using the casting method, core/shell NPs were successfully introduced to carboxymethyl cellulose sodium (CMC). The CMC nanocomposites displayed considerably broader optical response extending from near-ultraviolet to visible light, which was likely due to heterojunction between the p-CuO core and n-ZnO shell and defects originating from the synthetic process. The transmittance of pure CMC in the UV, visible, and near IR regions is significantly reduced with the addition of 2 and 4 wt% of CuO@ZnO core/shell NPs to CMC. 99% of UV light is absorbed when 4 wt% of CuO@ZnO core/shell NPs are added. The addition of different concentrations of CMC nanocomposite to one of the sunblock in Egyptian market were studied and showing the highest Sun Protection Factor of 22. Moreover, optical dispersion parameters and refractive index were improved strongly with core/shell NPs addition.

Molecular and biological activities of metal oxide-modified bioactive glass.

Bioactive glass (BG) was prepared by sol-gel method following the composition 60-([Formula: see text]) SiO2.34CaO.6P2O5, where x = 10 (FeO, CuO, ZnO or GeO). Samples were then studied with FTIR. Biological activities of the studied samples were processed with antibacterial test. Model molecules for different glass compositions were built and calculated with density functional theory at B3LYP/6-31 g(d) level. Some important parameters such as total dipole moment (TDM), HOMO/LUMO band gap energy (ΔE), and molecular electrostatic potential beside infrared spectra were calculated. Modeling data indicated that P4O10 vibrational characteristics are enhanced by the addition of SiO2.CaO due to electron rush resonating along whole crystal. FTIR results confirmed that the addition of ZnO to P4O10.SiO2.CaO significantly impacted the vibrational characteristics, unlike the other alternatives CuO, FeO and GeO that caused a smaller change in spectral indexing. The obtained values of TDM and ΔE indicated that P4O10.SiO2.CaO doped with ZnO is the most reactive composition. All the prepared BG composites showed antibacterial activity against three different pathogenic bacterial strains, with ZnO-doped BG demonstrating the highest antibacterial activity, confirming the molecular modeling calculations.

DFT and QSAR studies of PTFE/ZnO/SiO2 nanocomposite.

Polytetrafluoroethylene (PTFE) is one of the most significant fluoropolymers, and one of the most recent initiatives is to increase its performance by using metal oxides (MOs). Consequently, the surface modifications of PTFE with two metal oxides (MOs), SiO2 and ZnO, individually and as a mixture of the two MOs, were modeled using density functional theory (DFT). The B3LYPL/LANL2DZ model was used in the studies conducted to follow up the changes in electronic properties. The total dipole moment (TDM) and HOMO/LUMO band gap energy (∆E) of PTFE, which were 0.000 Debye and 8.517 eV respectively, were enhanced to 13.008 Debye and 0.690 eV in the case of PTFE/4ZnO/4SiO2. Moreover, with increasing nano filler (PTFE/8ZnO/8SiO2), TDM changed to 10.605 Debye and ∆E decreased to 0.273 eV leading to further improvement in the electronic properties. The molecular electrostatic potential (MESP) and quantitative structure activity relationship (QSAR) studies revealed that surface modification of PTFE with ZnO and SiO2 increased its electrical and thermal stability. The improved PTFE/ZnO/SiO2 composite can, therefore, be used as a self-cleaning layer for astronaut suits based on the findings of relatively high mobility, minimal reactivity to the surrounding environment, and thermal stability.

Design and implementation of humidity sensor based on carbon nitride modified with graphene quantum dots.

Relative humidity (RH) is one of the most important factors that deserve intensive study because of its impact on many aspects of life. In this work humidity sensor based on carbon nitride / graphene quantum dots (g-C3N4/GQDs) nanocomposites have been developed. The structure, morphology and composition properties of the g-C3N4/GQDs were investigated and analyzed by XRD, HR-TEM, FTIR, UV-Vis, Raman, XPS and BET surface area. The average particle size of GQDs was estimated from XRD to be 5 nm and confirmed using HRTEM. The HRTEM images prove that the GQDs are attached to the external surface of the g-C3N4. The measured BET surface area was found to be 216 m2/g, 313 m2/g, and 545 m2/g for GQDs, g-C3N4, and g-C3N4/GQDs respectively. The d-spacing and crystallite size were estimated from XRD and HRTEM and found in a good matching. The humidity sensing behavior of g-C3N4/GQDs was measured in a wide span of humidity from 7% up to 97% RH under different testing frequencies. The obtained results demonstrate good reversibility and fast response/recovery time. The implemented sensor exhibits a great application prospect in humidity alarm devices, automatic diaper alarms, and breath analysis, which have advantages such as strong anti-interference capability, low cost, and easy to use.

Structural and UV-blocking properties of carboxymethyl cellulose sodium/CuO nanocomposite films.

Nanoparticles have made a substantial contribution to the field of skincare products with UV filters in preserving human skin from sun damage. The current study aims to create new polymer nanocomposite filters for the efficient block of UV light that results from the stratospheric ozone layer loss. The casting approach was used to add various mass fractions of copper oxide nanoparticles (CuO-NPs) to a solution of carboxymethyl cellulose (CMC). The amorphous nature of CMC was revealed by XRD analysis, with the intensity of the typical peak of virgin polymer in the nanocomposite spectrum decreasing dramatically as the doping amount was increased. The FTIR spectra revealed the functional groups of CMC and the good interaction between the CMC chain and CuO-NPs. Optical experiments revealed that the optical transmittance of pure CMC was over 80%, whereas it dropped to 1% when CuO-NPs content was increased to 8 wt.%. Surprisingly, the inclusion of CuO-NPs considerably improved the UV blocking property of the films extended from the UV region (both UV-A: 320-400 nm and UV-B: 280-320 nm) to the visible region. Optical band gap of CMC decreased sharply with increasing CuO concentration. The tunable optical characteristics can be utilized in UV- blocking filters and various optoelectronics applications.

Effect of CuO and Graphene on PTFE Microfibers: Experimental and Modeling Approaches.

The surface of pure polytetrafluoroethylene (PTFE) microfibers was modified with ZnO and graphene (G), and the composite was studied using ATR-FTIR, XRD, and FESEM. FTIR results showed that two significant bands appeared at 1556 cm-1 and 515 cm-1 as indications for CuO and G interaction. The SEM results indicated that CuO and G were distributed uniformly on the surface of the PTFE microfibers, confirming the production of the PTFE/CuO/G composite. Density functional theory (DFT) calculations were performed on PTFE polymer nanocomposites containing various metal oxides (MOs) such as MgO, Al2O3, SiO2, TiO2, Fe3O4, NiO, CuO, ZnO, and ZrO2 at the B3LYP level using the LAN2DZ basis set. Total dipole moment (TDM) and HOMO/LUMO bandgap energy ΔE both show that the physical and electrical characteristics of PTFE with OCu change to 76.136 Debye and 0.400 eV, respectively. PTFE/OCu was investigated to observe its interaction with graphene quantum dots (GQDs). The results show that PTFE/OCu/GQD ZTRI surface conductivity improved significantly. As a result, the TDM of PTFE/OCu/GQD ZTRI and the HOMO/LUMO bandgap energy ΔE were 39.124 Debye and ΔE 0.206 eV, respectively. The new electrical characteristics of PTFE/OCu/GQD ZTRI indicate that this surface is appropriate for electronic applications.

Electronic and physical studies for Teflon FEP as a thermal control in low earth orbit reinforced with ZnO and SiO2 nanoparticles.

Fluorinated ethylene propylene (Teflon FEP) was used as external layer thermal insulator for Hubble Space Telescope (HST) and on the outside surfaces of space crafts in the low earth orbit (LEO). Teflon FEP was eroding as a result of exposure to atomic oxygen (AO) and different electromagnetic waves such as ultraviolet radiation and X-ray. Model molecules were used to simulate Teflon FEP and its interaction with other nanoparticles such as ZnO and SiO2. Density functional theory (DFT) was used to calculate model structures using B3LYP/LAN2DZ model. Molecular electrostatic potential as contour, band gap energy, and total dipole moment were computed for all models. Thermal stability properties were also studied for Teflon FEP both individually and interacted with ZnO and SiO2. Results showed that a layer of OZn and SiO2 on Teflon FEP, especially Teflon FEP + OZn + OSiO structure, improves the physical, chemical, thermal, and electrical stability of Teflon FEP, potentially acting as a corrosion-inhibiting layer.

Probing protein rejection behavior of blended PES-based flat-sheet ultrafiltration membranes: A density functional theory (DFT) study.

Membrane fouling is a common problem in membrane technology and causes detrimental effects for the applied membranes such as loss of integrity and productivity. Henceforward, we devoted this work to fabricate membranes that pose favored criteria in the direction of alleviating membrane fouling incidence. Herein, the fabricated membranes were traced via an assortment of both experimental and molecular modeling verifications to understand the mechanism of interaction. To do so, firstly, three different ultrafiltration (UF) membranes had been prepared via facile wet phase inversion method thru dipping a casting solution composed of polyethersulfone-polyvinyl pyrrolidone (PES-PVP) and polyethersulfone-Pluronic P31R1 (PES-P31R1) in a water coagulation bath. Regarding the practical-based data, the pristine PES membrane exhibited the highest rejection of bovine serum albumin (BSA) protein (model foulant) compared with the modified PES-based membranes. The membrane chemical compositions were elucidated with ATR-FTIR Spectroscopy. On the other hand, molecular modeling has been carried out via calculating thermodynamic parameters, level parametric method, and density functional theory (DFT). Thermodynamic parameters analysis indicated that the noticeable difference of BSA rejection may be ascribed to different entropy behavior for the fabricated membranes. In addition, the level parametric method (PM6) and density functional theory DFT: B3LYP with 6-31g (d,p) basis set models clarified the interaction manner of BSA molecules to membrane surfaces.

Green Route for the Removal of Pb from Aquatic Environment.

AIM AND OBJECTIVE: Wastewater treatment/remediation is a very important process that has a great environmental and economic impact. Therefore, it is crucial to innovate different methods to remove pollutants of different sources from wastewater. This work was conducted in order to study the removal of lead (Pb+2) from wastewater using microspheres of composites of sodium alginate, cellulose and chitosan, as well as using a cost-effective green route through composites of sodium alginate and dried water hyacinth. MATERIALS AND METHODS: Molecular modeling at B3LYP/6-31g(d,p) was utilized to study sodium alginate, cellulose and chitosan. Sodium alginate was cross-linked with calcium chloride to form microspheres, then both sodium alginate/cellulose and sodium alginate/chitosan were also crosslinked as 50/50 to form microspheres. The roots of the aquatic plant water hyacinth in dry form were added to the cross-linked sodium alginate for up to 70%. SEM and FTIR were employed to study the surface of the prepared microspheres and their structures respectively. Atomic absorption spectroscopy was used to study the levels of Pb. RESULTS: Molecular modeling indicated that the blending of such structures enhances their ability to bind with surrounding molecules owing to their ability to form hydrogen bonds. SEM results indicated that homogeneous structures of cellulose and chitosan are deformed when blended with sodium alginate, and FTIR confirmed the proper formation of the desired blends. Microspheres from sodium alginate showed the ability to remove Pb+2 from wastewater. SEM indicated further deformation in the morphology with the roughness of sodium alginate/water hyacinth microspheres, while FTIR confirmed the uniform matrices of the microspheres. The removal of Pb+2 was enhanced because of the addition of dried water hyacinth's roots. CONCLUSION: Modeling, experimental and kinetic data highlight sodium alginate/water hyacinth root as a green route to remediate Pb+2 from wastewater.

Spectroscopic analyses and genotoxicity of dioxins in the aquatic environment of Alexandria.

Dioxins have global concerns because of the bioaccumulation tendency and persistency in the environment. Water, seabream Pagrus auratus and seabass Dicentrarchus labrax samples were collected from Abu Qir, Alexandria to evaluate the concentration of dioxin. Fourier Transform Infrared Spectrometer (FTIR) and molecular modeling was applied for elucidating the molecular structure of fish samples. Furthermore, HPLC with UV detection was used to determine the concentration of dioxins (2,8-dichloro dibenzo-p-dioxin). RT-PCR assay was conducted to verify the expression of some immune genes in the fish species as a result of water pollution. The average detected concentrations varied from 0.2 to 1.3µg/l. Gene expression revealed that MHC class 1 and C3 were highly upregulated in liver and muscle of seabass and seabream while T2BP was highly regulated in seabass liver and seabream muscle and seabass muscle for transferrin, FTIR and molecular modeling indicate that dioxin finds its way to fish protein.

Preparation and Characterization of Novel Polyaniline Nanosensor for Sensitive Detection of Formaldehyde.

Nanomaterials are promising in the field of optical sensors due to their unique properties. Emeraldine base of polyaniline (Nano EB-PANI) was prepared, characterized and applied as an optical formaldehyde sensor. FTIR data confirm the formation of the EB-PANI. TEM and SEM revealed the size and shape of the nanoscale EB-PANI. XRD showed that the obtained nano EB-PANI has a partial crystalline nature. The sensing mechanism is based on the reaction of formaldehyde with Nano EB-PANI- to form a complex as described by molecular modeling HF/3-21G** level of theory. Results showed that Nano EB-PANI- detect low concentrations of formaldehyde ranging from 0.0003 to 0.9 ppm in a dose-dependent manner. The molecular modeling theory analysis showed that formaldehyde could interact with the amine of EB-PANI in, ring 3 or 4 or both together. The binding energy and dipole moment of the interaction between formaldehyde and polyaniline nanosensor were calculated by HF/3-21g** level of theory. The interaction with ring 3-NH gives a less stable product with a high dipole moment 6.978 Debye comparing with 1.678 Debye for the product of formaldehyde interaction with the terminal ring 4-NH. The development of such novel EB-PANI nanosensor can be used as, reliable and sensitive formaldehyde sensor.

Spectroscopic analyses of the photocatalytic behavior of nano titanium dioxide.

Nano titanium dioxide TiO2 was synthesized using hydrolysis method then subjected to several characterizations. XRD revealed that the as-prepared sample is pure anatase phase and after calcinations at 500°C for 3 h the crystallinity has increased. The crystallite size calculated by Debye-Scherrer's formula is 8 nm. The HRTEM image shows an average size of about 9 nm, which is close to the XRD calculation from Scherrer's formula. PM3 semiempirical quantum mechanical calculations were conducted to present the electronic as well as thermal properties for TiO2. FTIR spectra between 800 and 400 cm(-1) are the verification for the lattice vibrations of anatase TiO2. The photo catalytic degradation of methylene blue (MB) was tested by the prepared nano TiO2. Results indicate that, the maximum degradation efficiency reached 94.4% after 120 min of UV irradiation. This increase in the degradation efficiency of TiO2 could be attributed to the reduction in particle size that enhanced the crystallinity as a result of heat treatment.

A novel structure for removal of pollutants from wastewater.

Dried water hyacinth was subjected to molecular modifications using quantum mechanical calculations. The model simulates the modified plant as 3 cellulose units, one lignin and some metal oxides namely CaO; FeO and Al(OH)3 are attached through O-Linkage. The model suggests the ability to remove inorganic pollutants from wastewater according to unique hydrogen bonding and high total dipole moment. Based on this model microspheres are synthesized in the laboratory from dried water hyacinth and chitosan following self-assembly method. FTIR spectrum of microspheres exhibits only the characteristic bands for raw materials which give strong evidence that the formed material is a composite. The analysis of SEM micrographes of microspheres showed that the fibers of water hyacinth are imbedded in the crosslinked chitosan matrix. Batch adsorption kinetic models revealed that the sorption of lead ions on microsphere was very fast and the equilibrium was rapidly attained within 30 min. and properly correlated with the second-order kinetic model. Different models of isotherm sorption were used to describe the Pb (II) adsorption onto microspheres. From Langmuir isotherm, the maximum adsorption capacity (q(max)) for Pb(II) was 312.5 mg/g, which is about 3 times higher than that of the crude hyacinth. The free energy (E) was 15.798 kJ/mol which shows that the sorption process is endothermic and the mechanism of reaction is an ion-exchange. Even after four cycles of adsorption-desorption, the adsorption capacity was maintained and the decline in efficiency was less than 10%.