Investigation of MO Adsorption Kinetics and Photocatalytic Degradation Utilizing Hollow Fibers of Cu-CuO/TiO2 Nanocomposite.

This comprehensive study explores the kinetics of adsorption and its photocatalytic degradation of methyl orange (MO) using an advanced copper-decorated photocatalyst in the form of hollow fibers (HFs). Designed to boost both adsorption capacity and photocatalytic activity, the photocatalyst was tested in batch experiments to efficiently remove MO from aqueous solutions. Various isotherm models, including Langmuir, Freundlich, Sips, Temkin, and Dubinin-Radushkevich, along with kinetic models like pseudo-first and pseudo-second order, Elovich, Bangham, and Weber-Morris, were utilized to assess adsorption capacity and kinetics at varying initial concentrations. The results indicated a favorable MO physisorption on the nanocomposite photocatalyst under specific conditions. Further analysis of photocatalytic degradation under UV exposure revealed that the material maintained high degradation efficiency and stability across different MO concentrations. Through the facilitation of reactive oxygen species generation, oxygen played a crucial role in enhancing photocatalytic performance, while the degradation process following the Langmuir-Hinshelwood model. The study also confirmed the robustness and sustained activity of the nanocomposite photocatalyst, which could be regenerated and reused over five successive cycles, maintaining 92% of their initial performance at concentrations up to 15 mg/L. Overall, this effective nanocomposite photocatalyst structured in the form of HF shows great promise for effectively removing organic pollutants through combined adsorption and photocatalysis, offering valuable potential in wastewater treatment and environmental remediation.

Carbon Nanodisks Decorated with Guanidinylated Hyperbranched Polyethyleneimine Derivatives as Efficient Antibacterial Agents.

Non-toxic carbon-based hybrid nanomaterials based on carbon nanodisks were synthesized and assessed as novel antibacterial agents. Specifically, acid-treated carbon nanodisks (oxCNDs), as a safe alternative material to graphene oxide, interacted through covalent and non-covalent bonding with guanidinylated hyperbranched polyethyleneimine derivatives (GPEI5K and GPEI25K), affording the oxCNDs@GPEI5K and oxCNDs@GPEI25K hybrids. Their physico-chemical characterization confirmed the successful and homogenous attachment of GPEIs on the surface of oxCNDs, which, due to the presence of guanidinium groups, offered them improved aqueous stability. Moreover, the antibacterial activity of oxCNDs@GPEIs was evaluated against Gram-negative E. coli and Gram-positive S. aureus bacteria. It was found that both hybrids exhibited enhanced antibacterial activity, with oxCNDs@GPEI5K being more active than oxCNDs@GPEI25K. Their MIC and MBC values were found to be much lower than those of oxCNDs, revealing that the GPEI attachment endowed the hybrids with enhanced antibacterial properties. These improved properties were attributed to the polycationic character of the oxCNDs@GPEIs, which enables effective interaction with the bacterial cytoplasmic membrane and cell walls, leading to cell envelope damage, and eventually cell lysis. Finally, oxCNDs@GPEIs showed minimal cytotoxicity on mammalian cells, indicating that these hybrid nanomaterials have great potential to be used as safe and efficient antibacterial agents.

Comparative Study of the U(VI) Adsorption by Hybrid Silica-Hyperbranched Poly(ethylene imine) Nanoparticles and Xerogels.

Two different silica conformations (xerogels and nanoparticles), both formed by the mediation of dendritic poly (ethylene imine), were tested at low pHs for problematic uranyl cation sorption. The effect of crucial factors, i.e., temperature, electrostatic forces, adsorbent composition, accessibility of the pollutant to the dendritic cavities, and MW of the organic matrix, was investigated to determine the optimum formulation for water purification under these conditions. This was attained with the aid of UV-visible and FTIR spectroscopy, dynamic light scattering (DLS), ζ-potential, liquid nitrogen (LN2) porosimetry, thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). Results highlighted that both adsorbents have extraordinary sorption capacities. Xerogels are cost-effective since they approximate the performance of nanoparticles with much less organic content. Both adsorbents could be used in the form of dispersions. The xerogels, though, are more practicable materials since they may penetrate the pores of a metal or ceramic solid substrate in the form of a precursor gel-forming solution, producing composite purification devices.

Engineering Commercial TiO2 Powder into Tailored Beads for Efficient Water Purification.

In this study, efficient commercial photocatalyst (Degussa P25) nanoparticles were effectively dispersed and stabilized in alginate, a metal binding biopolymer. Taking advantage of alginate's superior metal chelating properties, copper nanoparticle-decorated photocatalysts were developed after a pyrolytic or calcination-sintering procedure, yielding ceramic beads with enhanced photocatalytic and mechanical properties, excellent resistance to attrition, and optimized handling compared to powdered photocatalysts. The morphological and structural characteristics were studied using LN2 porosimetry, SEM, and XRD. The abatement of an organic pollutant (Methyl Orange, MO) was explored in the dark and under UV irradiation via batch experiments. The final properties of the photocatalytic beads were defined by both the synthesis procedure and the heat treatment conditions, allowing for their further optimization. It was found that the pyrolytic carbon residuals enabled the adhesion of the TiO2 nanoparticles, acting as binder, and increased the MO adsorption capacity, leading to increased local concentration in the photocatalyst vicinity. Well dispersed Cu nanoparticles were also found to enhance photocatalytic activity. The prepared photocatalysts exhibited increased MO adsorption capacity (up to 3.0 mg/g) and also high photocatalytic efficiency of about 50% MO removal from water solutions, reaching an overall MO rejection of about 80%, at short contact times (3 h). Finally, the prepared photocatalysts kept their efficiency for at least four successive photocatalytic cycles.

Structuring efficient photocatalysts into bespoke fiber shaped systems for applied water treatment.

In this study, structured photocatalytic systems were successfully developed by a facile method based on Alginate molds and a wet-spinning/cross-linking technique, yielding commercial photocatalyst (Degussa P25) in the form of all-ceramic hollow fibers (HFs). Taking advantage of alginate's exceptional sorption properties, copper augmented HFs were also developed. The structured photocatalysts were thoroughly characterised by a variety of techniques, including nitrogen adsorption, SEM/EDS, XRD, XPS and Raman. Synthesis and heat treatment parameters were found to affect the fibers' properties, allowing their optimization. Treatment at 600 °C under Ar was found to produce the best performing photocatalysts in terms mechanical stability, resistance to attrition and photocatalytic performance. Ca-Alginate precursors led to structures with increased mechanical stability, while Cu-Alginate decorated the surface of the photocatalyst with highly dispersed copper nanoparticles, in the state of metallic and CuO. The developed materials were photo-catalytically active, while the copper decorated ceramic HFs exhibited the highest MO adsorption and photocatalytic degradation performance, reaching a MO removal of 73.4%. The synergestic effect of adsorption on the MO degradation performance was also noticed. Moreover, the copper addition facilitated the photocatalytic process by improving the electron-hole separation and inhibiting the recombination effects. The presence of carbon residue was also beneficial, enhancing the MO sorption on the photocatalysts. It is noteworthy that the structured photocatalysts retained their efficiency for at least four photocatalytic cycles. The prepared ceramic HFs exhibited enhanced mechanical properties and excellent resistance to attrition after subsequent cycles, rendering them excellent candidates for application in industrial wastewater processes.

Multi-Walled Carbon Nanotubes Decorated with Guanidinylated Dendritic Molecular Transporters: An Efficient Platform for the Selective Anticancer Activity of Doxorubicin.

An efficient doxorubicin (DOX) drug delivery system with specificity against tumor cells was developed, based on multi-walled carbon nanotubes (MWCNTs) functionalized with guanidinylated dendritic molecular transporters. Acid-treated MWCNTs (oxCNTs) interacted both electrostatically and through hydrogen bonding and van der Waals attraction forces with guanidinylated derivatives of 5000 and 25,000 Da molecular weight hyperbranched polyethyleneimine (GPEI5K and GPEI25K). Chemical characterization of these GPEI-functionalized oxCNTs revealed successful decoration with GPEIs all over the oxCNTs sidewalls, which, due to the presence of guanidinium groups, gave them aqueous compatibility and, thus, exceptional colloidal stability. These GPEI-functionalized CNTs were subsequently loaded with DOX for selective anticancer activity, yielding systems of high DOX loading, up to 99.5% encapsulation efficiency, while the DOX-loaded systems exhibited pH-triggered release and higher therapeutic efficacy compared to that of free DOX. Most importantly, the oxCNTs@GPEI5K-DOX system caused high and selective toxicity against cancer cells in a non-apoptotic, fast and catastrophic manner that cancer cells cannot recover from. Therefore, the oxCNTs@GPEI5K nanocarrier was found to be a potent and efficient nanoscale DOX delivery system, exhibiting high selectivity against cancerous cells, thus constituting a promising candidate for cancer therapy.

Cytotoxicity Effects of Water-Soluble Multi-Walled Carbon Nanotubes Decorated with Quaternized Hyperbranched Poly(ethyleneimine) Derivatives on Autotrophic and Heterotrophic Gram-Negative Bacteria.

Oxidized multi-walled carbon nanotubes (oxCNTs) were functionalized by a simple non-covalent modification procedure using quaternized hyperbranched poly(ethyleneimine) derivatives (QPEIs), with various quaternization degrees. Structural characterization of these hybrids using a variety of techniques, revealed the successful and homogenous anchoring of QPEIs on the oxCNTs' surface. Moreover, these hybrids efficiently dispersed in aqueous media, forming dispersions with excellent aqueous stability for over 12 months. Their cytotoxicity effect was investigated on two types of gram(-) bacteria, an autotrophic (cyanobacterium Synechococcus sp. PCC 7942) and a heterotrophic (bacterium Escherichia coli). An enhanced, dose-dependent antibacterial and anti-cyanobacterial activity against both tested organisms was observed, increasing with the quaternization degree. Remarkably, in the photosynthetic bacteria it was shown that the hybrid materials affect their photosynthetic apparatus by selective inhibition of the Photosystem-I electron transport activity. Cytotoxicity studies on a human prostate carcinoma DU145 cell line and 3T3 mouse fibroblasts revealed that all hybrids exhibit high cytocompatibility in the concentration range, in which they also exhibit both high antibacterial and anti-cyanobacterial activity. Thus, QPEI-functionalized oxCNTs can be very attractive candidates as antibacterial and anti-cyanobacterial agents that can be used for potential applications in the disinfection industry, as well as for the control of harmful cyanobacterial blooms.

Heavy metal sorption by calcium alginate beads from Laminaria digitata.

Alginate with a high M/G ratio, extracted from Laminaria digitata, was evaluated for Cu(2+), Cd(2+) and Pb(2+) sorption in acidic solutions, in the form of calcium cross-linked beads. The high M/G ratio of alginate extracted from this algal species is most likely the determining factor for the increased adsorption capacity of the investigated metals, indicating that the mannuronic acid is responsible for the ion exchange mechanism. The data obtained from the batch experiments have been interpreted with Langmuir, Freundlich and Sips models. The Sips equation provided the best fit with the experimental results, indicating sorption sites heterogeneity for the material. The pH was found to have a significant effect on the process, with sorption capacity reaching a maximum at pH 4.5, indicating a competition mechanism between H(+) and metal ions. Kinetic experiments were performed at the optimum pH. For the interpretation of the kinetic experiments the Linear Adsorption Model was employed and diffusion coefficients were determined. The model fits the experimental data at higher concentrations, where the adsorbed quantity remains almost constant. Finally, a simplified expression of the batch kinetic adsorption model was employed. The model, predicts adequately, not only the diffusivity values, but also the concentration profiles inside the spherical particles.

Modified in situ antimicrobial susceptibility testing method based on cyanobacteria chlorophyll a fluorescence.

The chlorophyll a fluorescence based antimicrobial susceptibility testing (AST) method presented in a previous work was based on the measurement of Chl a fluorescence of the gram(-) cyanobacterium Synechococcus sp. PCC 7942. Synechococcus sp. PCC 7942 as a gram(-) bacterium is affected by antibacterial agents via mechanisms affecting all gram(-) bacteria, however, as an exclusively phototrophic organism it would also be affected by photosynthesis inhibitory action of an agent that otherwise has no antibacterial properties. In this report, the method is modified by replacing the exclusively phototrophic Synechococcus sp. PCC 7942 with the Synechocystis sp. PCC 6714, capable of both phototrophic and heterotrophic growth in order to add versatility and better reflect the antibacterial effects of surfaces under study towards nonphotosynthetic bacteria.

An in situ antimicrobial susceptibility testing method based on in vivo measurements of chlorophyll α fluorescence.

Up to now antimicrobial susceptibility testing (AST) methods are indirect and generally involve the manual counting of bacterial colonies following the extraction of microorganisms from the surface under study and their inoculation in a separate procedure. In this work, an in situ, direct and instrumental method for the evaluation and assessment of antibacterial properties of materials and surfaces is proposed. Instead of indirectly determining antibacterial activity using the typical gram(-) test organisms with the subsequent manual colony count or inhibition zone measurement, the proposed procedure, employs photosynthetic gram(-) cyanobacteria deposited directly onto the surface under study and assesses cell proliferation and viability by a quick, accurate and reproducible instrumental chlorophyll fluorescence spectrophotometric technique. In contrast with existing methods of determination of antibacterial properties, it produces high resolution and quantitative results and is so versatile that it could be used to evaluate the antibacterial properties of any compound (organic, inorganic, natural or man-made) under any experimental conditions, depending on the targeted application.

Facile synthesis of carbon supported copper nanoparticles from alginate precursor with controlled metal content and catalytic NO reduction properties.

A copper-nanoparticle-doped carbon was prepared from an alginate based precursor in a one step carbonisation-reduction procedure based on the modified polyol process. The ion exchange capacity of the precursor as well as the porosity, metal content, thermal properties, of the final product, were investigated. The preparation route leads to a porous carbon/copper composite with predefined metal loading reaching up to over 30% (w/w) of finely dispersed Cu nanoparticles of fairly uniform size. NO catalytic abatement evaluation showed high efficiency even at low temperatures compared to other recently reported carbon supported catalysts.

Metal-carboxylate interactions in metal-alginate complexes studied with FTIR spectroscopy.

FTIR spectroscopy was used in order to obtain information about metal-carboxylate interactions in metal-alginate complexes of alginic acid and sodium alginate from the brown algae Laminaria digitata after crosslinking with Ca(2+), Cu(2+), Cd(2+), Zn(2+), Ni(2+) and Pb(2+). From the frequencies of the characteristic peaks for asymmetric COO stretching vibration (nu(asym)(COO(-)) and symmetric COO stretching vibration (nu(sym)(COO(-))) a 'pseudo bridged' unidentate coordination with intermolecular hydrogen bonds is proposed for the metal-carboxylate complexes in polyguluronic regions while for the polymannuronic regions the bidentate bridging coordination was proposed. The PIB factor introduced previously as a relationship between metal sorption and frequencies of the asymmetric vibrations was found not to correlate with sorption capacity or any other physical property of the metal-alginate complexes studied.