Rapid in-situ growth of enzyme-mimicking Pd nanoparticles on TEMPO-oxidized nanocellulose for the efficient detection of ascorbic acid.

Rapid, efficient and green method of Pd nanoparticles (PdNPs) synthesis on TEMPO-oxidized cellulose nanofibril (TCNF) is demonstrated here. The nanohybrid (PdNPs/TCNF) exhibited peroxidase and oxidase-like activities evident by the oxidation of three chromogenic substrates. Enzyme kinetic studies using 3,3',5,5'-Tetramethylbenzidine (TMB) oxidation uncovered the excellent kinetic parameters (low Km and high Vmax) and good specific activities of 215 U/g and 107 U/g for peroxidase and oxidase-like activities, respectively. A colorimetric assay for ascorbic acid (AA) detection is proposed based on its ability to reduce oxidized TMB to its colorless form. However, presence of nanozyme caused re-oxidation of TMB to its blue colored form within few minutes resulting in time limitation and inaccurate detection. Thanks to the film forming nature of TCNF; this limitation was overcome by employing PdNPs/TCNF film strips that can be easily removed before AA addition. The assay allowed AA detection in the linear range of 0.25-10 µM with a detection limit of 0.039 µM. The results of AA detection in commercial beverages and vitamin C tablets are matching with the specified values. Further the nanozyme exhibited high tolerance to pH (2-10) and temperature (up to 80 °C) and good recyclability for five cycles.

Synthesis of Cu-doped carbon dot/chitosan film composite as a catalyst for the colorimetric detection of hydrogen peroxide and glucose.

The use of colloidal nanoparticles suffers from the drawbacks of potential color interference and substrate-induced aggregation. To overcome the limitations, a catalyst was developed by crosslinking Cu-doped carbon dots (Cu-CDs) with chitosan. Cu-CDs with high peroxidase activity were prepared by using a rapid microwave-assisted method. The Cu-CDs containing 6.88% of Cu had an average particle size of 2.25 nm and exhibited 9% of fluorescence quantum yield. The nanozyme/film composite was prepared by crosslinking between the amino groups of Cu-CDs and those of chitosan via a glutaraldehyde linker. A H2O2-mediated tetramethylbenzidine (TMB) oxidation reaction was use to evaluate the peroxidase activity of the film. Based on the TMB color changes, colorimetric assays were developed for the detection of H2O2 and glucose at an absorption wavelength 652 nm. Under the optimal conditions, the linear ranges for H2O2 and glucose were 0.625-40 µM and 1.9-125 µM, respectively, and the detection limits were 0.12 µM and 0.69 µM, respectively. The colorimetric assay was also applied to analyze diluted human serum samples spiked with glucose. Furthermore, this biodegradable, non-toxic, and easy-to-handle nanozyme composite could be stored for over 4 weeks without a significant decrease in activity.

Effective fabrication of cellulose nanofibrils supported Pd nanoparticles as a novel nanozyme with peroxidase and oxidase-like activities for efficient dye degradation.

Nanozyme-based dye degradation methods are promising for the remediation of water pollution. Though Pd nanoparticles (PdNPs) are known to act as nanozymes, their dye degradation capability has not been investigated. Low nanozyme activities, easy aggregation, difficulties in recovery and reuse are the major challenges in achieving this. For the first time, cellulose nanofibrils-supported PdNPs (PdNPs/PCNF) as a novel nanozyme with good peroxidase and oxidase-mimicking activities and easy recyclability is explored for dye degradation. An efficient and rapid method of PdNPs/PCNF preparation was demonstrated by adjusting the pH and microwave irradiation. Enzyme kinetic studies revealed good kinetic parameters and specific activities of 415 and 277 U/g for peroxidase and oxidase, respectively. PdNPs/PCNF offered 99.64% degradation of methylene blue within 12 min (0.468 min-1) with 0.4 M H2O2 at pH 5.0. Mechanistic studies revealed the involvement of hydroxyl and superoxide radicals. Owing to the network-like structure of PCNF, films and foams were prepared, their dye degradation potentials were compared, and recyclability was tested. Successful degradation of mixed dye solutions and spiked real water samples was achieved and a continuous flow method was demonstrated using a foam-packed column.

Gold nanoparticles spontaneously grown on cellulose nanofibrils as a reusable nanozyme for colorimetric detection of cholesterol in human serum.

Recently, gold nanoparticles (AuNPs) are extensively used as peroxidase mimics. However, low catalytic activity, high synthesis cost, substrate-induced aggregation in reaction medium and difficulty in recovery and reuse still remain as major challenges. Here, a novel, simple, spontaneous, and reagent-less in-situ method for the production of AuNPs using dialdehyde cellulose nanofibrils (DACNF) is proposed. AuNPs synthesis time and size were greatly influenced by aldehyde content and the optimal aldehyde content for ultra-small AuNPs (≈10 nm) was 2.1 mM/g. AuNPs@DACNFs exhibited broad-spectrum peroxidase activity and steady-state kinetics revealed their better kinetic parameters (low Km and high Vmax) over horseradish peroxidase (HRP). AuNPs@DACNFs was further converted into paper strip, which served as a biosensor for H2O2 and cholesterol detection. The proposed method exhibited wide linear response in the range of 10-90 µM and 0.05-0.45 mM, and detection limit of 0.39 µM and 1.9 µM for H2O2 and cholesterol, respectively. Great shelf life and reusability were evident by FE-SEM and ICP-OES analysis. The smartphone application "Color Grab" was used to enable the portable onsite detection. The results of cholesterol detection in human serum samples were in agreement with clinically observed values, suggesting the great potential of the probe in disease diagnosis.

Preparation and Characterization of Polybutylene Succinate Reinforced with Pure Cellulose Nanofibril and Lignocellulose Nanofibril Using Two-Step Process.

This study reports the preparation of a polybutylene succinate (PBS) film reinforced with pure cellulose nanofibril (PCNF) and lignocellulose nanofibril (LCNF) by a two-step process that consists of solvent dispersion and twin-screw extrusion. Compared to the conventional one-step process, this method offered improved mechanical properties. The addition of 5% CNF increased the tensile properties up to 18.8%. Further, the effect of the lignin content was also studied by using LCNF as a reinforcement. The LCNF was prepared with and without a deep eutectic solvent (DES) pretreatment to gain LCNF with a lignin content that varied between 5, 19, and 30%. The mechanical properties results show that a 5% addition of LCNF to the PBS matrix increased its tensile strength and elastic modulus. Further, the morphological and thermal properties of the composites were also studied in detail.

Wet-Spun Composite Filaments from Lignocellulose Nanofibrils/Alginate and Their Physico-Mechanical Properties.

Lignocellulose nanofibrils (LCNFs) with different lignin contents were prepared using choline chloride (ChCl)/lactic acid (LA), deep eutectic solvent (DES) pretreatment, and subsequent mechanical defibrillation. The LCNFs had a diameter of 15.3-18.2 nm, which was similar to the diameter of commercial pure cellulose nanofibrils (PCNFs). The LCNFs and PCNFs were wet-spun in CaCl2 solution for filament fabrication. The addition of sodium alginate (AL) significantly improved the wet-spinnability of the LCNFs. As the AL content increased, the average diameter of the composite filaments increased, and the orientation index decreased. The increase in AL content improved the wet-spinnability of CNFs but deteriorated the tensile properties. The increase in the spinning rate resulted in an increase in the orientation index, which improved the tensile strength and elastic modulus.

Preparation and Characterization of Cellulose Acetate Film Reinforced with Cellulose Nanofibril.

In this study, cellulose acetate (CA)/cellulose nanofibril (CNF) film was prepared via solvent casting. CNF was used as reinforcement to increase tensile properties of CA film. CNF ratio was varied into 3, 5, and 10 phr (parts per hundred rubbers). Triacetin (TA) and triethyl citrate (TC) were used as two different eco-friendly plasticizers. Two different types of solvent, which are acetone and N-methyl-2-pyrrolidone (NMP), were also used. CA/CNF film was prepared by mixing CA and CNF in acetone or NMP with 10% concentration and stirred for 24 h. Then, the solution was cast in a polytetrafluoroethylene (PTFE) dish followed by solvent evaporation for 12 h at room temperature for acetone and 24 h at 80 °C in an oven dryer for NMP. The effect of solvent type, plasticizers type, and CNF amount on film properties was studied. Good dispersion in NMP was evident from the morphological study of fractured surface and visible light transmittance. The results showed that CNF has a better dispersion in NMP which leads to a significant increase in tensile strength and elastic modulus up to 38% and 65%, respectively, compared with those of neat CA. CNF addition up to 5 phr loading increased the mechanical properties of the film composites.

Polyquaternium enhances the colloidal stability of chitosan-capped platinum nanoparticles and their antibacterial activity.

Here, for the first time, we have developed a novel green synthesis method where chitosan acts as a reducing agent and as a colloidal stabilizer, together with polyquaternium for the synthesis of platinum nanoparticles (PtNPs). It was observed that only chitosan-stabilized PtNPs (Ch@PtNPs) were stable up to pH 5, with a diameter of around 89 nm. The diameter of the Ch@PtNPs increased with the increase in pH, indicating the instability of Ch@PtNPs at neutral and alkaline mediums. However, when polyquaternium (PQ) (a cationic polymer) was added as a stabilizer along with chitosan, the diameter of chitosan/polyquaternium stabilized PtNPs (Ch/PQ@PtNPs), i.e. 87 nm, remained almost constant up to pH 9. Similarly, the pH-dependent decrease in the surface charge of Ch@PtNPs was also attenuated with the addition of polyquaternium. This indicates high colloidal stability of Ch/PQ@PtNPs in acidic, neutral, as well as alkaline mediums. It was observed that Ch/PQ@PtNPs exhibited high antibacterial activity againstStaphylococcus aureus, as compared to uncapped PtNPs and Ch@PtNPs. Thus, the addition of PQ increases the antibacterial properties of Ch/PQ@PtNPs againstStaphylococcus aureusby enhancing the stability of PtNPs at neutral pH.

Esterification of Lignin Isolated by Deep Eutectic Solvent Using Fatty Acid Chloride, and Its Composite Film with Poly(lactic acid).

In this study, the effect of lignin esterification with fatty acid chloride on the properties of lignin and lignin/poly(lactic acid) (PLA) composites was investigated. Lignocellulose (Pinus densiflora S. et Z.) was treated using a deep eutectic solvent (DES) with choline chloride (ChCl)/lactic acid (LA). From the DES-soluble fraction, DES-lignin (DL) was isolated by a regeneration process. Lignin esterification was conducted with palmitoyl chloride (PC). As the PC loading increased for DL esterification, the Mw of esterified DL (EDL) was increased, and the glass transition temperature (Tg) was decreased. In DL or EDL/PLA composite films, it was observed that EDL/PLA had cleaner and smoother morphological characteristics than DL/PLA. The addition of DL or EDL in a PLA matrix resulted in a deterioration of tensile properties as compared with neat PLA. The EDL/PLA composite film had a higher tensile strength and elastic modulus than the DL/PLA composite film. DL esterification decreased water absorption with lower water diffusion coefficients. The effect of lignin esterification on improving the compatibility of lignin and PLA was demonstrated. These results are expected to contribute to the development of high-strength lignin composites.

In-situ fabrication of novel flower like MoS2/CoTiO3 nanorod heterostructures for the recyclable degradation of ciprofloxacin and bisphenol A under sunlight.

Effectual degradation of toxic water contaminants is a crucial step in water purification and designing an efficient semiconductor based hybrid structure photocatalyst is a good approach to achieve this. Benefiting from the combination of semiconductors, a series of novel visible-light active flower-like MoS2/CoTiO3 nanorod heterostructures with excellent morphological contact interface were prepared through a facile in-situ hydrothermal process. These heterostructures were well characterized and demonstrated high photocatalytic performance for ciprofloxacin (CIP) and bisphenol A (BPA) under sunlight irradiation. Compared to pristine CoTiO3 and MoS2, the optimal catalyst (5 wt% MoS2/CoTiO3) presented 39.97 and 22.32 times higher activity for CIP degradation and 26.85 and 15.66 times higher activity for BPA degradation, respectively. This improved activity can be accounted for the effective interfacial contact which promotes the efficient charge carriers separation and reduce its recombination. The catalyst exhibited decent stability and was potentially reused for five cycles without significant loss in activity. Furthermore, based on active species scavenging experiments the plausible photodegradation mechanism is discussed in detail.

Shape recoverable, Au nanoparticles loaded nanocellulose foams as a recyclable catalyst for the dynamic and batch discoloration of dyes.

An environmental benign in-situ formation and growth of gold nanoparticles (AuNPs) on TEMPO-oxidized cellulose nanofibrils (TOCNF) is reported here. With the active functional groups (aldehyde and carboxyl), TOCNF served as a synchronized reducing and supporting agent for the formation of AuNPs. The entire synthesis process was completed within 30 s under microwave irradiation and regarded as ultra-fast. As obtained AuNPs@TOCNF nanohybrid suspension was freeze-dried to form strong water-activated shape recovery 3D foam. Internal morphology and porosity of the foam were studied by SEM and BET. AuNPs@TOCNF foams exhibited excellent catalytic activity for the discoloration of cationic and anionic dyes in batch and dynamic column processes. The spent foams can be easily recovered and reused up to five cycles with more than 98 % efficiency. During the catalytic processes, no obvious deterioration of the foam structure was observed. Practical applicability of the nanocatalyst was evaluated by treating spiked sea water sample.

Microwave-assisted preparation of a silver nanoparticles/N-doped carbon dots nanocomposite and its application for catalytic reduction of rhodamine B, methyl red and 4-nitrophenol dyes.

In the current work, a silver nanoparticles/nitrogen-doped carbon dots (AgNPs/NCDs) nanocomposite was prepared by a microwave-assisted method that does not require additional reducing or stabilizing agents. Multiple analytical techniques were used to characterize the prepared nanocomposite. The nanocomposite exhibited a surface plasmon resonance (SPR) absorption peak at 420 nm, indicating the development of AgNPs with NCDs. Further, HRTEM results confirmed the formation of the nanocomposite with the appearance of lattice fringes of both materials. Additionally, the nanocomposite did not show any precipitation even after two months of storage. The nanocomposite exhibited high catalytic activity towards the reduction of rhodamine B (RhB, 98.83%), methyl red (MR, 97.14%) and 4-nitrophenol (4-NP, 99.95%) at ambient temperature. Besides, the kinetic analysis revealed that the reduction reaction followed pseudo-first-order kinetics and the calculated rate constants (k) for rhodamine B (RhB), methyl red (MR) and 4-nitrophenol (4-NP) were found to be 0.0296 s-1, 0.0233 s-1 and 0.029 s-1, respectively. Moreover, it is a reusable and stable catalyst for reduction reactions up to five cycles without significant loss in catalytic activity. Finally, a plausible mechanism for the reduction of pollutants is also discussed in detail. As a whole, the prepared nanocomposite might display stunning behaviour for wastewater treatment applications.

Rapid in-situ growth of gold nanoparticles on cationic cellulose nanofibrils: Recyclable nanozyme for the colorimetric glucose detection.

Novel microwave-assisted green in-situ synthesis of positively charged gold nanoparticles (AuNPs) supported by cationic cellulose nanofibrils (C.CNF) within 30 s and devoid of additional reducing agent is reported. Peroxidase activity of these positive AuNPs was studied and that appeared to be superior over its negative charged counterpart. Further the AuNPs@C.CNF is casted into a film which makes it reusable. Using TMB substrate, simple and sensitive colorimetric detection methods for H2O2 and glucose were established. Under optimal conditions, the linear ranges were found to be 0.5-30 µM and 1-60 µM, and the detection limits were 0.30 and 0.67 µM for H2O2 and glucose, respectively. The film was potentially reused for the detection of glucose up to five cycles without a decrease in the activity. Further, this technique was employed to quantify glucose in human serum samples, and the obtained results were comparable with those of the standard GOD-POD method.

Rapid synchronous synthesis of Ag nanoparticles and Ag nanoparticles/holocellulose nanofibrils: Hg(II) detection and dye discoloration.

A novel microwave-assisted green method that synchronously synthesizes silver nanoparticles (AgNPs) and AgNPs decorated holocellulose nanofibrils (AgNPs/HCNF) within a minute and without using a reducing agent is reported. As obtained nanomaterials were well characterized using various analytical techniques. AgNPs applied as a colorimetric probe for the selective recognition of Hg(II) (linear range 10-200 µg L-1, detection limit 1.16 µg L-1). The probe was able to quantify Hg(II) in spiked tap, bore, and lake water samples and paper strips were developed to facilitate the onsite detection. Furthermore, freeze-drying of the AgNPs/HCNF nanocomposite produced aerogel that served as an excellent catalyst for the reduction of Congo red and methylene blue. The aerogel was easily recovered and reused without a decrease in activity or deterioration of its structure for five cycles. These results indicate the great potential of the AgNPs/HCNF aerogel for waste water treatment and catalytic applications.

Adsorption Characteristics of Ag Nanoparticles on Cellulose Nanofibrils with Different Chemical Compositions.

The adsorption characteristics of silver nanoparticles (AgNPs) on cellulose nanofibrils (CNFs) were investigated herein with different chemical compositions. Pure cellulose nanofibers (PCNFs), lignocellulose nanofibers (LCNFs) with different lignin contents (LCNF-20% and LCNF-31%), and holocellulose nanofibers (HCNFs) with hemicellulose were used in this study. Furthermore, CNFs and silver nitrate were mixed and reacted at different temperatures, and NaBH4 was used as the reducing agent. First, the effect of temperature on the adsorption of AgNPs on PCNF was studied. At an optimal temperature (45 °C), the effect of the chemical composition of CNF was studied. The overall properties were analyzed using UV-vis spectroscopy, transmission electron microscopy, X-ray diffraction, Fourier-transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The AgNPs were found to be spherical under all conditions with average diameter of 5.3 nm (PCNF), 5.6 nm (HCNF), 6.3 nm (LCNF-20%) and 6.6 nm (LCNF-31%). The amount of AgNPs adsorbed on the CNF was observed to vary, based on the chemical composition of the CNF. The adsorption amount of AgNPs was observed to increase in the order of LCNF-20% > PCNF > LCNF-31% > HCNF. The results indicated that phenolic hydroxyl groups present in LCNF significantly affected the adsorption of AgNPs.

N-Doped carbon dots with pH-sensitive emission, and their application to simultaneous fluorometric determination of iron(III) and copper(II).

Simultaneous fluorometric determination of iron(III) and copper(II) without the use of any masking agent or additional treatment is achieved by using N-doped carbon dots (NCDs). The NCDs were hydrothermally prepared, have strongest excitation/emission peaks at 320/406 nm and a 47% quantum yield. Excitation-tunable emission is found to depend on solution pH values. This supports the involvement of surface states in the origin of the excitation dependent nature. The NCDs were employed as a fluorescent probe for the simultaneous determination of Fe(III) with a linear response in the 3-60 µM concentration range and a 0.31 µM detection limit (LOD). The probe also responds linearly to Cu(II) in the 0.5-15 µM concentration range and with a 56 nM LOD. With the addition of Cu(II), the absorption spectra of NCDs presented a clear decrease in the intensity at 312 nm followed by an increase at 360 nm. This is not observed in the presence of Fe(III). The fluorescence lifetime of NCDs (5.8 ns) is reduced by Fe(III) but not by Cu(II). Thus, the two metal ions can be simultaneously detected without the need for any reagents. The probe was employed to quantify Fe(III) and Cu(II) in spiked water, serum, and urine samples. Graphical abstract Schematic representation of hydrothermal synthesis of highly fluorescent N-doped carbon dots with novel pH dependent emission and their application for the simultaneous determination of Cu(II) and Fe(III) with individual ion discrimination.

Construction of in situ self-assembled FeWO4/g-C3N4 nanosheet heterostructured Z-scheme photocatalysts for enhanced photocatalytic degradation of rhodamine B and tetracycline.

Although photocatalytic degradation is an ideal strategy for cleaning environmental pollution, it remains challenging to construct a highly efficient photocatalytic system by steering the charge flow in a precise manner. In this work, a novel, highly efficient, stable, and visible light active hybrid photocatalytic system consisting of FeWO4 and g-C3N4 nanosheets (CNNs) has been successfully prepared by an in situ self-assembly solvothermal approach. Several characterization techniques were employed to study the phase structures, morphologies, optical properties, surface composition and chemical state of the as-prepared samples. SEM and TEM results demonstrated that the FeWO4 nanoparticles are uniformly dispersed on the surface of CNNs with a diameter of about 10-20 nm, which could provide maximum interfacial contact and a synergistic coupling effect between FeWO4 and CNNs. XPS and FTIR results confirmed that there was strong electrostatic interaction between FeWO4 and CNNs, suggesting the formation of heterojunctions between them. In addition, UV-DRS and PL spectroscopy revealed that the FeWO4/CNN composites exhibited increased visible light absorption and improved charge generation/separation efficiency. As a result, the photocatalytic activity of the FeWO4/CNNs was enhanced in comparison with pure FeWO4 and CNNs for rhodamine B (RhB) and tetracycline (TC) degradation under natural sunlight irradiation. The photocatalytic efficiency of the optimal FeWO4/CNN composite (10 wt% FeWO4/CNNs) for the degradation of RhB (TC) was about 13.26 (4.95) and 86.2 (31.1) times higher than that of pure FeWO4 and CNNs, respectively. Meanwhile, the 10 wt% FeWO4/CNN sample exhibits good photocatalytic stability in recycling experiments. The enhanced photocatalytic activity may be attributed to the formation of the Z-scheme system between FeWO4 and CNNs, effectively prolonging the lifetime of the photoexcited electrons generated by CNNs and the photoexcited holes generated by FeWO4, which was subsequently confirmed by the active species trapping experiments and the calculation of relative band alignments. This work opens up a new feasible avenue to synthesize visible light active Z-scheme photocatalysts for application in energy production and environmental remediation.

Facile Conversion of Toxic Cigarette Butts to N,S-Codoped Carbon Dots and Their Application in Fluorescent Film, Security Ink, Bioimaging, Sensing and Logic Gate Operation.

The present work is emphasized on converting toxic cigarette butts (CBs) into highly fluorescent N,S-codoped carbon dots by a facile hydrothermal approach and exploring their multiple applications. The as-produced carbon dots (CBCDs) exhibited bright and stable fluorescence with a quantum yield of 26% and used as a label-free probe for "on-off-on" sequential detection of Fe3+ and ascorbic acid (AA). The fluorescence of CBCDs can be significantly quenched by Fe3+ ions through static quenching and restored upon the subsequent addition of AA due to the reduction of Fe3+ to Fe2+ by AA. This nanoprobe presented great selectivity and excellent sensitivity to Fe3+ and AA with a detection limit of 0.13 and 0.2 µM, respectively. Furthermore, the nanoprobe was extended to biosystem (intracellular detection) and successfully applied for the detection of Fe3+ in real water (tap, bore, and pond) and AA in biological samples (human urine and serum). In addition, we have constructed an IMPLICATION logic gate based on these unique sensing characteristics. The "visible-invisible" and "UV-visible" property explored their use as invisible ink for security applications. Furthermore, highly photostable fluorescent polymer films were prepared by incorporating CBCDs in poly(vinyl alcohol). It is anticipated that the strong and stable fluorescence emission nature of these films might find direct or indirect applications in various optical/optoelectronic devices, ranging from fluorescent displays to light-emitting diodes.

Green synthesis of highly fluorescent nitrogen - Doped carbon dots from Lantana camara berries for effective detection of lead(II) and bioimaging.

Here, we developed a simple green approach for the synthesis of highly fluorescent nitrogen doped carbon dots (NCDs) using Lantana camara berries. Optical and physicochemical properties of as synthesized NCDs were extensively studied by using various analytical techniques. NCDs exhibited bright fluorescence with Quantum yield as high as 33.15%, which is stable to various effects like heat, pH, ionic strength and continuous irradiation. Furthermore, the NCDs presented highly selective and sensitive fluorescence response towards Pb2+ which explored their potential to serve as a label-free fluorescent probe for the effective detection of Pb2+. As developed NCDs based probe exhibited a great linear response (R2=0.998) towards Pb2+ in the concentration range of 0-200nM with a detection limit of 9.64nM. The probe further presented high precision without any interference and was successfully applied for the detection of Pb2+ in the real water and human sera (serum and urine) samples. Cytotoxicity studies on both cancerous (human breast adenocarcinoma MCF-7) and normal (Human embryonic kidney HEK-293) cell lines revealed their excellent biocompatibility. With their low cytotoxicity, strong fluorescence and excitation-dependent emission, NCDs were successfully applied as multi-colour bioimaging agents and Pb2+ detection capabilities were further evaluated in live cells.