Nanotechnology is one of the most interesting areas of research due to its flexibility to improve or form new products from nanoparticles (NPs), and as a fast, greener, more eco-friendly and sustainable solution to technological and environmental challenges. Among metal oxides of photocatalytic performance, the use of titania (TiO2) as photocatalyst is most popular due to its unique optical and electronic properties. Despite the wide utilization, the synthesis of TiO2 NPs bears many disadvantages: it utilizes various less environmental-friendly chemicals, high cost, requires high pressure and energy, and potentially hazardous physical and chemical methods. Hence, the development of green synthesis approach with eco-friendly natural products can be used to overcome these adverse effects. In this work, TiO2 NPs have been prepared by using Deinbollia pinnata leaves extracts, obtained by different solvents (n-hexane, ethyl acetate, and ethanol) with different polarities. The extracts acted as the reducing agent, while titanium isopropoxide as the precursor and water as the solvent. X-ray diffraction (XRD) pattern confirmed the synthesized TiO2 consist of anatase phase in high purity, with average crystallite size in the range of 19-21 nm. Characterization by using field emission scanning electron microscopy (FESEM) showed the TiO2 NPs possess a uniform semi-spherical shape in the size range of 33-48 nm. The energy dispersive X-ray (EDX) spectra of green TiO2 NPs showed two peaks for the main elements of Ti (61 Wt.%) and O (35 Wt.%). The band-gap energy of 3.2 eV was determined using UV-Vis spectroscopy. From the nitrogen sorption analysis, type V isotherm of the material was obtained, with BET surface area of 31.77 m2/g. The photocatalytic activity of synthesized TiO2 was evaluated for photodegradation of methyl orange (MO) under UV light irradiation. Based on the results, it is shown that TiO2 NPs synthesized with D. pinnata leaves extracted using ethyl acetate showed the most effective photodegradation performance, achieving 98.7% of MO conversion within 150 min. It can be concluded that the use of plant extracts in synthesis with TiO2 managed to produce highly crystalline anatase TiO2 with superior photocatalytic activity in the photodegradation of organic dye.
The study reports the preparation of a composite consisting of magnetite coated with nanosilica extracted from oil palm leaves (OPL) ash as nanosupports for immobilization of Candida rugosa lipase (CRL) and its application for the synthesis of butyl butyrate. Results of immobilization parameters showed that ∼ 80% of CRL (84.5 mg) initially offered was immobilized onto the surface of the nanosupports to yield a maximum protein loading and specific activity of 67.5 ± 0.72 mg/g and 320.8 ± 0.42 U/g of support, respectively. Surface topography, morphology as well as information on surface composition obtained by Raman spectroscopy, atomic force microscopy, field emission scanning electron microscopy and transmission electron microscopy showed that CRL was successfully immobilized onto the nanosupports, affirming its biocompatibility. Under optimal conditions (3.5 mg/mL protein loading, at 45 ℃, 3 h and molar ratio 2:1 (1-butanol:n-butyric acid) the CRL/Gl-A-SiO2-MNPs gave a maximum yield of 94 ± 0.24% butyl butyrate as compared to 84 ± 0.32% in the lyophilized CRL. CRL/Gl-A-SiO2-MNPs showed an extended operational stability, retaining 50% of its initial activity after 17 consecutive esterification cycles. The results indicated that OPL derived nanosilica coated on magnetite can potentially be employed as carrier for lipase immobilization in replacement of the non-renewable conventionalsilica sources.
The past decade has observed a significant surge in efforts to discover biological systems for the fabrication of metal nanoparticles. Among these methods, plant-mediated synthesis has garnered sizeable attention due to its rapid, cost-effective, environmentally benign single-step procedure. This study explores a step-wise, room-temperature protocol for the synthesis of gold nanoparticles (AuNPs) using Carallia brachiata, a mangrove species from the west coast of Peninsular Malaysia. The effects of various reaction parameters, such as incubation time, metal ion concentration, amount of extract and pH, on the formation of stable colloids were monitored using UV-visible (UV-Vis) absorption spectrophotometry. Our findings revealed that the physicochemical properties of the AuNPs were significantly dependent on the pH. Changing the pH of the plant extract from acidic to basic appears to have resulted in a blue-shift in the main characteristic feature of the surface plasmon resonance (SPR) band, from 535 to 511 nm. The high-resolution-transmission electron microscopy (HR-TEM) and field emission scanning electron microscopy (FESEM) images revealed the morphologies of the AuNPs synthesized at the inherent pH, varying from isodiametric spheres to exotic polygons and prisms, with sizes ranging from 10 to 120 nm. Contrarily, an optimum pH of 10 generated primarily spherical-shaped AuNPs with narrower size distribution (8-13 nm). The X-ray diffraction (XRD) analysis verified the formation of AuNPs as the diffraction patterns matched well with the standard value of a face-centered cubic (FCC) Au lattice structure. The Fourier-transform infrared (FTIR) spectra suggested that different functional groups are involved in the biosynthetic process, while the phytochemical test revealed a clear role of the phenolic compounds. The reduction of 4-nitrophenol (4-NP) was selected as the model reaction for evaluating the catalytic performance of the green-synthesized AuNPs. The catalytic activity of the small, isotropic AuNPs prepared using basic aqueous extract was more effective than the nanoanisotrops, with more than 90% of 4-NP conversion achieved in under an hour with just 3 mg of the nanocatalyst.
Herein, this study extracted nanocrystalline cellulose (NC) and silica (SiO2) from raw oil palm leaves (OPL), and employed as nanofillers in polyethersulfone (PES) to produce NC-SiO2-PES as support to immobilize Candida rugosa lipase (CRL) (NC-SiO2-PES/CRL). XRD, TGA-DTG and FTIR-ATR data affirmed that NC and SiO2 were isolated from OPL with corresponding crystallinity indices of 68 % and 70 %. A 0.02 cm membrane size with 5% (w/v) of NC-SiO2 without PVP K30 was optimal for membrane fabrication. CRL immobilized on the Glut-AP-NC-SiO2-PES membrane gave a higher conversion of pentyl valerate (PeVa) (91.3 %, p < 0.05) compared to Glut-NC-SiO2-PES (73.9 %) (p < 0.05). Characterization of the NC-SiO2-PES/CRL biocatalyst verified the presence of CRL. Hence, raw OPL is a proven good source of NC and SiO2, as reinforcement nanofillers in PES. The overall findings envisage the promising use of NC-SiO2-PES/CRL to catalyze an expedient and high yield of PeVa, alongside the suitability of NC-SiO2-PES for activating other enzymes.
Currently, the chemically-assisted esterification to manufacture butyl butyrate employs corrosive homogeneous acid catalyst and liberates enormous quantities of hazardous by-products which complicate downstream treatment processes. This study aimed to identify the optimized esterification conditions, and the kinetic aspects of the enzyme-assisted synthesis of butyl butyrate using immobilized Candida rugosa lipase activated by chitosan-reinforced nanocellulose derived from raw oil palm leaves (CRL/CS-NC). The best process variables that gave the maximum conversion degree of butyl butyrate by CRL/CS-NC (90.2%) in just 3 h, as compared to free CRL (62.9%) are as follows: 50 °C, 1:2 M ratio of acid/alcohol, stirring rate of 200 rpm and a 3 mg/mL enzyme load. The enzymatic esterification followed the ping pong bi-bi mechanism with substrate inhibition, revealing a ˜1.1-fold higher Ki for CRL/CS-NC (55.55 mM) over free CRL (50.68 mM). This indicated that CRL/CS-NC was less inhibited by the substrates. Butanol was preferred over butyric acid as reflected by the higher apparent Michaelis-Menten constant of CRL/CS-NC for butanol (137 mM) than butyric acid (142.7 mM). Thus, the kinetics data conclusively showed that CRL/CS-NC (Vmax 0.48 mM min-1, Keff 0.07 min-1 mM-1) was catalytically more efficient than free CRL (Vmax 0.35 mM min-1, Keff 0.06 min-1 mM-1).
The contribution of chitosan/nanocellulose (CS-NC) to the enzymatic activity of Candida rugosa lipase covalently bound on the surface of CS-NC (CRL/CS-NC) was investigated. Cellulosic material from oil palm frond leaves (OPFL) were bleached, alkaline treated and acid hydrolyzed to obtain the purified NC and used as nano-fillers in CS. XRD, Raman spectroscopy and optical fluorescence microscopic analyses revealed existence of strong hydrogen bonds between CS and the NC nanofillers. The CRLs were successfully conjugated to the surface of the CS-NC supports via imine bonds that occurred through a Schiff's based mechanism. Process parameters for the immobilization of CRL were assessed for factors temperature, concentration of glutaraldehyde and pH, to afford the highest enzyme activity to achieve maximum conversion of butyl butyrate within 3h of incubation. Conversion as high as 88% was reached under an optimized condition of 25°C, 0.3% glutaraldehyde concentration and buffer at pH7. Thermal stability of CRL/CS-NCs was 1.5-fold greater than that of free CRL, with biocatalysts reusability for up to 8 successive esterification cycles. This research provides a promising approach for expanding the use of NC from OPFL for enhancing enzyme activity in favour of an alternative eco-friendly means to synthesize butyl butyrate.
The demonstration of the structure-properties relationship of shape-dependent photocatalysts remains a challenge today. Herein, one-dimensional (1-D)-like titania (TiO2), as a model photocatalyst, has been synthesized under a strong magnetic field in the presence of a magnetically responsive liquid crystal as the structure-aligning agent to demonstrate the relationship between a well-aligned structure and its photocatalytic properties. The importance of the 1-D-like TiO2 and its relationship with the electronic structures that affect the electron-hole recombination and the photocatalytic activity need to be clarified. The synthesis of 1-D-like TiO2 with liquid crystal as the structure-aligning agent was carried out using the sol-gel method under a magnetic field (0.3 T). The mixture of liquid crystal, 4'-pentyl-4-biphenylcarbonitrile (5CB), tetra-n-butyl orthotitanate (TBOT), 2-propanol, and water, was subjected to slow hydrolysis under a magnetic field. The TiO2-5CB took a well-aligned whiskerlike shape when the reaction mixture was placed under the magnetic field, while irregularly shaped TiO2-5CB particles were formed when no magnetic field was applied. It shows that the strong interaction between 5CB and TBOT during the hydrolysis process under a magnetic field controls the shape of titania. The intensity of the emission peaks in the photoluminescence spectrum of 1-D-like TiO2-5CB was lowered compared with the TiO2-5CB synthesized without the magnetic field, suggesting the occurrence of electron transfer from 5CB to the 1-D-like TiO2-5CB during ultraviolet irradiation. Apart from that, direct current electrical conductivity and Hall effect studies showed that the 1-D-like TiO2 composite enhanced electron mobility. Thus, the recombination of electrons and holes was delayed due to the increase in electron mobility; hence, the photocatalytic activity of the 1-D-like TiO2 composite in the oxidation of styrene in the presence of aqueous hydrogen peroxide under UV irradiation was enhanced. This suggests that the 1-D-like shape of TiO2 composite plays an important role in its photocatalytic activity.
In this study, nanocellulose (NC) was successfully extracted from oil palm frond leaves (OPFL) using a combination of bleaching, alkaline treatment and acid hydrolysis. X-ray diffractogram revealed the extracted NC was crystalline with a crystallinity index of 70.2%. This indicates its suitability as nano-fillers for preparing the chitosan/nanocellulose (CS-NC) supports to immobilize Candida rugosa lipase (CRL) to produce the CRL/CS-NC biocatalysts. FTIR, FESEM and TGA characterizations of the CRL/CS-NC confirm the CRLs were successfully conjugated to the CS-NC supports. The air-dried CS-NC supports gave satisfactory immobilization of the CRLs (5.2mg/g) with the resultant CRL/CS-NCs catalysed conversions of ≥80% of butyl butyrate within 6h. Time course reaction profile revealed that 76.3% butyl butyrate conversion was achieved at 4h immobilization time using 3mg/mL of CRL/CS-NCs. NMR analyses on the purified butyl butyrate confirmed that the ester was successfully synthesized.
The use of chemical materials to tackle environmental concerns has undergone significant evolution, particularly in the pursuit of strategies for removing pollutants from wastewater as part of environmental remediation an increasingly crucial research topic. Employing green photocatalysts stands out as an efficient and cost-effective approach, playing a key role in promoting sustainable environmental remediation. This study introduces the modification of zinc oxide with cobalt chromite (CoCr2O4/ZnO) through a green synthesis method employing Basella alba L. leaves extract (BALE). Utilizing various characterization techniques, including FT-IR, UV-Vis DRS, XRD, SEM-EDS, and TEM, key features of ZnO, CoCr2O4, and CoCr2O4/ZnO nanocomposites were identified. The optical band gaps for ZnO, CoCr2O4, and CoCr2O4/ZnO nanocomposites were determined as 3.16, 1.71, and 2.80 eV, respectively, where it was shown that the band gap of the ZnO was reduced significantly. CoCr2O4/ZnO nanocomposites displayed a cubic shape of CoCr2O4 on the surface of ZnO, with a particle size of 23.84 ± 8.08 nm. The photocatalytic activity was assessed through the degradation of malachite green under visible light irradiation, where the CoCr2O4/ZnO nanocomposites exhibited superior photodegradation efficiency at 90.91%, surpassing ZnO alone (57.09%). This improvement in photocatalytic activity is attributed to a reduced band gap energy and a high rate constant value of 9.57 × 10-3 min-1, demonstrating pseudo-first-order reaction kinetics. In summary, this research presents the development of a ZnO-based photocatalyst with exceptional performance, especially in the visible light spectrum, making it a promising candidate for applications in wastewater removal.
Depression is a common mental disorder that may lead to major mental health problems, and antidepressant drugs have been used as a treatment of choice to mitigate symptoms of major depressive disorders by ameliorating the chemical imbalances of neurotransmitters in brain. Since abusing antidepressant drugs such as selective serotonin reuptake inhibitors and tricyclic antidepressant drugs can cause severe adverse effects, continuous toxicological monitoring of the parent compounds as well as their metabolites using numerous analytical methods appears pertinent. Among them, capillary electrophoresis has been popularly utilized since the method has a lot of advantages viz. using small amounts of sample and solvents, ease of operation, and rapid analysis. This review paper brings a survey of more than 30 papers on capillary electrophoresis of antidepressant drugs published approximately from 1999 until 2018. It focuses on the reported capillary electrophoresis techniques and their applications and challenges for determining antidepressant drugs and their metabolites. It is organized according to the commonly used capillary zone electrophoresis method, followed by non-aqueous capillary electrophoresis and micellar electrokinetic chromatography, with details on breakthrough findings. Where available, information is given about the background electrolyte used, detector utilized, and sensitivity obtained.