Recycled Jute Non-Woven Material Coated with Polyaniline/TiO2 Nanocomposite for Removal of Heavy Metal Ions from Water.

Growing volumes of textile waste and heavy metal pollution of water are emerging environmental challenges. In an attempt to tackle these issues, a non-woven sorbent based on jute fibers was fabricated by recycling the textile waste from the carpet industry. The influence of contact time, concentration, pH and temperature on the sorption of lead and copper ions from aqueous solutions was studied. In order to enhance the sorption capacity of the non-woven material, in situ synthesis of polyaniline (PANI) in the presence of TiO2 nanostructures was performed. The contribution of TiO2 nanoparticles and TiO2 nanotubes to the uniformity of PANI coating and overall sorption behavior was compared. Electrokinetic measurements indicated increased swelling of modified fibers. FTIR and Raman spectroscopy revealed the formation of the emeraldine base form of PANI. FESEM confirmed the creation of the uniform nanocomposite coating over jute fibers. The modification with PANI/TiO2 nanocomposite resulted in a more than 3-fold greater sorption capacity of the material for lead ions, and a 2-fold greater absorption capacity for copper ions independently of applied TiO2 nanostructure. The participation of both TiO2 nanostructures in PANI synthesis resulted in excellent cover of jute fibers, but the form of TiO2 had a negligible effect on metal ion uptake.

Postindustrial Jute Waste as a Support for Nano-Carbon Nitride Photocatalyst: Influence of Chemical Pretreatment.

Non-woven jute (NWJ) produced from carpet industry waste was oxidized by H2O2 or alkali-treated by NaOH and compared with water-washed samples. Changes in the structure of the NWJ, tracked by X-ray diffraction (XRD), showed that both chemical treatments disrupt hydrogen bond networks between cellulose Iß chains of the NWJ fibers. Thereafter, nano-carbon nitride (nCN) was impregnated, using a layer-by-layer technique, onto water-washed jute samples (nCN-Jw), NaOH-treated samples (nCN-Ja) and-H2O2 treated samples (nCN-Jo). Analysis of the Fourier transform infrared spectroscopy (FTIR) spectra of the impregnated samples revealed that nCN anchors to the water-washed NWJ surface through hemicellulose and secondary hydroxyl groups of the cellulose. In the case of chemically treated samples, nCN is preferentially bonded to the hydroxymethyl groups of cellulose. The stability and reusability of prepared nCN-jute (nCN-J) samples were assessed by tracking the photocatalytic degradation of Acid Orange 7 (AO7) dye under simulated solar light irradiation. Results from up to ten consecutive photocatalytic cycles demonstrated varying degrees of effectiveness across different samples. nCN-Jo and nCN-Ja samples exhibited declining effectiveness over cycles, attributed to bond instability between nCN and jute. In contrast, the nCN-Jw sample consistently maintained high degradation rates over ten cycles, with a dye removal percentage constantly above 90%.

Antibacterial activity of Cu-based nanoparticles synthesized on the cotton fabrics modified with polycarboxylic acids.

The fabrication of antimicrobial textile nanocomposite by in situ synthesis of Cu-based nanoparticles on cotton fabrics modified with different polycarboxylic acids was discussed in this study. In order to evaluate the influence of carboxyl group content on Cu2+-ions adsorption, their subsequent reduction with sodium borohydride and formation of Cu-based nanoparticles, cotton fabrics were modified with succinic, citric and 1,2,3,4-butanetetracarboxylic acids. It was shown that the larger the number of carboxyl groups in applied acid, the larger the content of free carboxyl groups on the fibers and consequently, the larger the Cu2+-ions uptake and total amounts of Cu-based nanoparticles. On the basis of the XPS and XRD measurements, it was suggested that synthesized nanoparticles were mixture of Cu2O and CuO. Fabricated nanocomposites provided maximum reduction of Gram-negative bacterium E. coli and Gram-positive bacterium S. aureus and controlled release of Cu2+-ions in physiological saline solution which are necessary prerequisites for infection prevention.

Photocatalytic decomposition of selected biologically active compounds in environmental waters using TiO2/polyaniline nanocomposites: Kinetics, toxicity and intermediates assessment.

A comprehensive study of the removal of selected biologically active compounds (pharmaceuticals and pesticides) from different water types was conducted using bare TiO2 nanoparticles and TiO2/polyaniline (TP-50, TP-100, and TP-150) nanocomposite powders. In order to investigate how molecular structure of the substrate influences the rate of its removal, we compared degradation efficiency of the initial substrates and degree of mineralization for the active components of pharmaceuticals (propranolol, and amitriptyline) and pesticides (sulcotrione, and clomazone) in double distilled (DDW) and environmental waters. The results indicate that the efficiency of photocatalytic degradation of propranolol and amitriptyline was higher in environmental waters: rivers (Danube, Tisa, and Begej) and lakes (Moharac, and Sot) in comparison with DDW. On the contrary, degradation efficacy of sulcotrione and clomazone was lower in environmental waters. Further, of the all catalysts applied, bare TiO2 and TP-100 were found to be most effective in the mineralization of propranolol and amitriptyline, respectively, while TP-150 appeared to be the most efficient in terms of sulcotrione and clomazone mineralization. Also, there was no significant toxicity observed after the irradiation of pharmaceuticals or pesticides solutions using appropriate catalysts on rat hepatoma (H-4-II-E), mouse neuroblastoma (Neuro-2a), human colon adenocarcinoma (HT-29), and human fetal lung (MRC-5) cell lines. Subsequently, detection and identification of the formed intermediates in the case of sulcotrione photocatalytic degradation using bare TiO2 and TP-150 showed slightly different pathways of degradation. Furthermore, tentative pathways of sulcotrione photocatalytic degradation were proposed and discussed.

Biodegradation of cotton and cotton/polyester fabrics impregnated with Ag/TiO2 nanoparticles in soil.

This study discusses the biodegradation behavior of cotton and cotton/PET fabrics impregnated with Ag/TiO2 nanoparticles in soil. Biodegradation behavior was evaluated by standard test method ASTM 5988-03 based on determination of percentage conversions of carbon content to CO2 as well as by soil burial test and enzymatic hydrolysis with cellulase where the extent of biodegradation was estimated by the calculation of fabric weight loss. The morphological and chemical changes of fibers during biodegradation process were analyzed by SEM and FTIR spectroscopy, respectively. The results obtained by all applied methods suggested that Ag/TiO2 nanoparticles hindered the biodegradation of investigated cotton and cotton/PET fabrics. Soil burial test indicated faster biodegradation of the impregnated blend compared to impregnated cotton fabric which is attributed to smaller amount of fabricated Ag nanoparticles on the blend proved by AAS measurement. Similar trend was established by enzymatic hydrolysis of cotton fibers. Severe damage of cotton fibers in both fabrics due to biodegradation process was confirmed by SEM. However, the cotton fiber damage occurred to a lesser extent in the samples that were impregnated with Ag/TiO2 nanoparticles. PET fibers remained intact which was also indicated by FTIR analysis.

SALDI-TOF-MS analyses of small molecules (citric acid, dexasone, vitamins E and A) using TiO2 nanocrystals as substrates.

Surface-assisted laser desorption/ionisation time-of-flight mass spectrometry (SALDI-TOF-MS) might be the method of choice for the analysis of low mass molecules (less than m/z 500). Titanium dioxide (TiO2) nanocrystals as a substrate for SALDI-TOF-MS improve the reproducibility of the signal intensities and prevent the fragmentation of some molecules upon laser irradiation, as we have previously shown. In addition, variously shaped and sized TiO2 nanocrystals/substrates for SALDI-MS could be used for quantification of small molecules, which are otherwise difficult to detect with the assistance of organic matrices. TiO2-assisted LDI-MS spectra could be acquired with excellent reproducibility and repeatability and with low detection limit. In the current study, we analysed the spectra of dexasone, citric acid, vitamin E and vitamin A acquired with TiO2 nanocrystals of various shapes and dimensions, i.e. the colloidal TiO2 nanoparticles (TiO2 NPs), TiO2 prolate nanospheroids (TiO2 PNSs) and TiO2 nanotubes (TiO2 NTs). Various shapes and dimensions of substrates were used since these factors determine desorption and ionisation processes. The homogeneity on the target plate was compared based on signal-to-noise values of peaks of interest of analysed molecules as well as the within-day and day-to-day repeatability. In summary, the obtained results show that the applicability of individual TiO2 nanocrystals depends on the analyte. Signals which are acquired with the assistance of TiO2 PNSs have the highest sensitivity and reproducibility (the smallest standard deviation), even compared with those in the LDI mode. This implies that TiO2 PNSs could also be suitable for quantitative analyses of small molecules.

Sonophotocatalytic degradation of dye C.I. Acid Orange 7 by TiO2 and Ag nanoparticles immobilized on corona pretreated polypropylene non-woven fabric.

This study discusses the possibility of using corona pre-treated polypropylene (PP) non-woven fabric as a support for immobilization of colloidal TiO2 and Ag nanoparticles in order to remove dye C.I. Acid Orange 7 from aqueous solution. Dye removal efficiency by sonocatalysis, photocatalysis and sonophotocatalysis was evaluated on corona pre-treated fabric loaded with TiO2 nanoparticles, corona pre-treated fabric double loaded with TiO2 nanoparticles and corona pre-treated fabrics loaded with TiO2 nanoparticles before and after deposition of Ag nanoparticles. In addition, the stability of PP non-woven fabric during these processes was investigated. The substrates were characterized by SEM, EDX and AAS analyses. The change of the dye concentration was evaluated by UV-VIS spectrophotometry. Unlike sonocatalysis and photocatalysis, complete dye removal from both solution and non-woven fabric was obtained already after 240-270 min of sonophotocatalysis. Corona pre-treated PP non-woven fabric loaded with Ag nanoparticles prior to deposition of TiO2 nanoparticles provided excellent degradation efficiency and superior reusability. Sonophotocatalytic degradation of dye in the presence of all investigated samples was the most prominent in acidic conditions. Although this nanocomposite system ensured fast discoloration of dye solution, TOC values of water measured after sonophotocatalysis were not satisfactory because of PP degradation. Therefore, it is suggested to include TOC evaluation in each case study where different supports for TiO2 nanoparticles are used since these nanoparticles may guarantee the dye removal from solution but the stability of support could be problematic causing even more serious environmental impact.

Surface modification of anatase nanoparticles with fused ring salicylate-type ligands (3-hydroxy-2-naphthoic acids): a combined DFT and experimental study of optical properties.

The surface modification of nanocrystalline TiO2 particles (45 Å) with salicylate-type ligands consisting of an extended aromatic ring system, specifically 3-hydroxy-2-naphthoic acid, 3,5-dihydroxy-2-naphthoic acid and 3,7-dihydroxy-2-naphthoic acid, was found to alter the optical properties of nanoparticles in a similar way to salicylic acid. The formation of the inner-sphere charge-transfer (CT) complexes results in a red shift of the semiconductor absorption compared to unmodified nanocrystallites and a reduction in the band gap upon the increase in the electron delocalization when including an additional ring. The investigated ligands have the optimal geometry for binding to surface Ti atoms, resulting in ring coordination complexes of a salicylate-type (binuclear bidentate binding-bridging) thus restoring the six-coordinated octahedral geometry of surface Ti atoms. From both absorption measurements in methanol/water = 90/10 solutions and steady-state quenching measurements of modifier fluorescence upon binding to TiO2 in aqueous solutions, stability constants in the order of 10(3) M(-1) have been determined at pH 2 and pH 3. Fluorescence lifetime measurements, in the presence and absence of colloidal TiO2 nanoparticles, indicated that the fluorescence quenching process is primarily static quenching, thus proving the formation of a nonfluorescent CT complex. The binding structures were investigated by using FTIR spectroscopy. Quantum chemical calculations on model systems using density functional theory (DFT) were performed to obtain the vibrational frequencies of charge transfer complexes, and the calculated values were then compared with the experimental data.

Colloidal TiO2 nanoparticles as substrates for M(S)ALDI mass spectrometry of transition metal complexes.

RATIONALE: Nanoparticles as substrates for matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) have advantages over organic matrices, since they enable acquisition of spectra in the low-mass range. It has been previously shown that TiO(2) nanoparticles can be used as substrate for MALDI-TOF MS analysis of phospholipids and for other types of molecules, but none of them was applied to the analysis of transition metal complexes. METHODS: The MALDI-TOF mass spectra of potential anti-tumor drugs [AuCl(2)(bipy)]Cl, [PtCl(4)(bipy)], and [RuCl(2)(bipy)(2) ]Cl acquired with organic matrices have been compared with spectra acquired with colloidal titanium dioxide nanoparticles. Colloidal TiO(2) nanoparticles (NPs) with average diameter of 5 nm were synthesized and characterized by microscopy. For some experiments, the TiO(2) NPs were treated at 60 °C. Suspensions of matrix and the analyte were premixed, applied to the MALDI target and left at room temperature. Mass spectra were acquired with a 50-Hz pulsed nitrogen laser emitting at a wavelength of 337 nm. RESULTS: The MALDI spectra of transition metal complexes acquired with TiO(2) NPs exhibited somewhat lower sensitivity than those with organic matrices; on the other hand, they are characterized by significantly lower number of signals arising from the tested complexes than the organic matrices. Whereas adducts between organic matrices and the analytes were detectable in the spectra, this was not the case for the TiO(2)-assisted mass spectra. CONCLUSIONS: We have shown that colloidal TiO(2) NPs can be used as substrates for MALDI-TOF MS of transition metal complexes. Although the sensitivity of this approach in comparison with the use of organic matrices might still be a problem, the potential of the applications of NPs for the mass spectrometric characterization of transition metal complexes is clearly demonstrated.

Surface modification of anatase nanoparticles with fused ring catecholate type ligands: a combined DFT and experimental study of optical properties.

Surface modification of nanocrystalline TiO(2) particles (45 Å) with catecholate-type ligands consisting of an extended aromatic ring system, i.e., 2,3-dihydroxynaphthalene and anthrarobin, was found to alter the optical properties of the nanoparticles in a similar way to modification with catechol. The formation of inner-sphere charge-transfer (CT) complexes results in a red shift of the semiconductor absorption compared to unmodified nanocrystallites and the reduction of the band gap upon the increase of the electron delocalization on the inclusion of additional rings. The binding structures were investigated by FTIR spectroscopy. The investigated ligands have the optimal geometry for binding to surface Ti atoms, resulting in ring coordination complexes of catecholate type (binuclear bidentate binding-bridging) thus restoring the six-coordinated octahedral geometry of surface Ti atoms. From the Benesi-Hildebrand plot, stability constants in methanol/water = 90/10 solutions at pH 2 of the order 10(3) M(-1) have been determined. Quantum chemical calculations on model systems using density functional theory (DFT) were performed to obtain vibrational frequencies of charge transfer complexes, and the calculated values were compared with the experimental data.

Improved properties of oxygen and argon RF plasma-activated polyester fabrics loaded with TiO2 nanoparticles.

The potentials of low-pressure capacitively coupled RF oxygen and argon plasmas for the activation of polyester fibers surface that can enhance the deposition of colloidal TiO(2) nanoparticles were discussed. SEM and XPS analysis confirmed the plasma-induced morphological and chemical changes on the surface of polyester fibers. Oxygen and argon plasma pretreated polyester fabrics loaded with TiO(2) nanoparticles provided maximum reduction of Gram-negative bacteria E. coli and UV blocking. The self-cleaning effects tested on blueberry juice stains and photodegradation of methylene blue in aqueous solution proved excellent photocatalytic activity of TiO(2) nanoparticles deposited onto fiber surface. Although both plasmas significantly contributed to overall improvement of properties of such nanocomposite textile material, oxygen plasma treatment, in particular, enhanced the deposition of colloidal TiO(2) nanoparticles and thus ensured superior effects.

New Hybrid Properties of TiO(2) Nanoparticles Surface Modified With Catecholate Type Ligands.

Surface modification of nanocrystalline TiO(2) particles (45 A) with bidentate benzene derivatives (catechol, pyrogallol, and gallic acid) was found to alter optical properties of nanoparticles. The formation of the inner-sphere charge-transfer complexes results in a red shift of the semiconductor absorption compared to unmodified nanocrystallites. The binding structures were investigated by using FTIR spectroscopy. The investigated ligands have the optimal geometry for chelating surface Ti atoms, resulting in ring coordination complexes (catecholate type of binuclear bidentate binding-bridging) thus restoring in six-coordinated octahedral geometry of surface Ti atoms. From the Benesi-Hildebrand plot, the stability constants at pH 2 of the order 10(3) M(-1) have been determined.

Optical properties of shaped silver nanoparticles.

The influence of shape and dielectric property of surrounding media on surface plasmon absorption band of silver nanoparticles was studied. Spherical silver nanoparticles (d = 5.6 nm) synthesized in water using NaBH4 as a reducing agent are transferred in non-polar solvent (chloroform) with phase-transfer reagent oleylamine. The absorption spectrum of oleylamine-capped silver nanoparticles dispersed in chloroform shows a strong surface plasmon resonance band that is 19 nm red-shifted compared to unmodified particles in water. The values for peak position and corresponding half widths are compared with theoretical calculations based on Mie theory. Prismatic and plate-like silver nanoparticles were synthesized in water using trisodium citrate as a reducing agent and cetyltrimethylammonium bromide as stabilizer. Due to structural anisotropy of prismatic and plate-like silver nanoparticles three surface plasmon resonance bands were observed in absorption spectrum. Nanocomposites consisting of non-spherical silver nanoparticles and polyvinyl alcohol exhibit different optical properties compared to water colloid. Instead of three surface plasmon bands, nanocomposite film has only one peak at 460 nm. Reason for appearance of single surface plasmon resonance band in nanocomposite film was discussed according to Maxwell-Garnet theory.

Complex and charge transfer between TiO2 and pyrroloquinoline quinone.

Pyrroloquinoline quinone (PQQ) forms a tridentate complex with coordinatively unsaturated titanium atoms on the surface of approximately 4.5 nm TiO2 particles; an association constant of K = 550 M-1 per Ti(IV)surf has been determined. Low-temperature electron paramagnetic resonance was employed in identification of localized charges and consequently produced radicals and in determination of charge-transfer processes. The photoexcitation of the PQQ-TiO2 complex results in the transfer of conduction band electrons from TiO2 to bound PQQ and the formation of the semiquinone radical. Attaching dopamine (DA) as an electron donor and PQQ as an electron acceptor on the surface of TiO2 results in spatial separation of photogenerated charges; the holes localize on dopamine and electrons on PQQ, with higher yields than for each component separately. In this triad-type assembly (PQQ-TiO2/DA) the PQQ that is bound to the particles acts as a sink for electrons allowing their almost complete scavenging even at temperature as low as 4 K.

Charge separation and surface reconstruction: a Mn2+ doping study.

Hydrothermal synthesis of Mn doped anatase (TiO2) nanoparticles using scrolled nanotubes of TiO2 and MnCl2 as the starting materials is described. Incorporation of Mn2+ ions on the substitutional sites was confirmed using X-ray absorption fine structure (FT-XAFS) while the oxidation state Mn(II) and coordination environment were determined using both electron paramagnetic resonance (EPR) and X-ray absorption near edge spectroscopy (XANES). Two different hyperfine couplings of 96 and 86 G were found using high-field (130 GHz) EPR reporting that Mn atoms occupy two distinct sites: one undercoordinated (reconstructed surface) and the other octahedral crystalline geometry (nanoparticle core), respectively. It was found that Mn atoms that occupy surface layers are weakly bound to the anatase lattice and can be easily leached using simple dialysis, while those incorporated in the nanoparticle core are bound more strongly and cannot be removed by dialysis. Light excitation EPR reveals that Mn ions incorporated in the surface layers participate in the charge separation, while those trapped deeply in the nanoparticle core do not show any photoactivity. Doping of the core of nanoparticles with Mn2+ ions, on the other hand, enables synthesis of optically transparent films having superparamagnetic behavior at room temperatures with a saturation magnetic moment of 1.23 microB per Mn atom.

Surface states of titanium dioxide nanoparticles modified with enediol ligands.

Control of surface states of titanium dioxide nanoparticles using 2-(3,4-dihydroxyphenyl)ethylamine (dopamine) and 3,4-dihydrophenylacetic acid, which act as ligands to the undercoordinated surface sites (carrier traps), is demonstrated by electrochemical techniques. The deepest traps were found to be most reactive and are selectively removed by the addition of the ligands which enhances the kinetics of electron accumulation in the film. Furthermore, a shift in the Fermi level to more positive potentials was detected for electrodes modified with the negatively charged ligand (3,4-dihydrophenylacetic acid) compared to that of electrodes modified with the positively charged ligand (dopamine). The presence of the negative charge on the ligand also contributed to the underpotential of hydrogen evolution on 3,4-dihydrophenylacetic acid-modified electrodes.

Assembly and charge transfer in hybrid TiO(2) architectures using biotin-avidin as a connector.

Exploiting the presence of undercoordinated surface Ti atoms at the tips of TiO2 nanorods and the dopamine selectivity for these Ti surface states, biotin was conjugated to TiO2 nanocrystallites using dopamine as a bridging linker. Using abiotin-avidin complex as a connector the "tip-to-tip" assembly of 400 nm elongated TiO2 rods was obtained. The photoexcitation of avidin-TiO2 hybrids resulted in the transfer of holes from nanocrystallites to protein and consequent oxidation of avidin, most probably at tyrosine 33.