One of the most crucial attributes of synthetic organic chemistry is to design organic reactions under the facets of green chemistry for the sustainable production of chemicals. Thus, due to the intensified environmental and safety concern, the need for new technologies for conducting chemical transformation has grown. In this regard, there is enormous interest in the use of heterogeneous catalysts as they generally avoid the generation of waste, require fewer toxic reagents, as well as entail easier separation and recycling of the catalyst. α,β-Unsaturated acids have been widely used in various industrial applications and have been identified as one of the most promising chemicals obtained via the Knoevenagel condensation reaction. This review aims to discuss the most pertinent heterogeneous catalytic systems such as zeolites, mesoporous silica, ionic liquids, metal oxides, and graphitic carbon nitride-based catalysts in the Knoevenagel reaction. Ultimately, this review focuses not only on the catalyst but also provides an overall idea and guide for the preparation of new catalysts with outstanding properties by looking at the chemical and engineering aspects such as the reaction conditions and the mechanisms.
Over the last decade, interest in the utilization of solar energy for photocatalysis treatment processes has taken centre-stage. Researchers had focused on doping TiO2 with SiO2 to obtain an efficient degradation rate of various types of target pollutants both under UV and visible-light irradiation. In order to further improve this degradation effect, some researchers resorted to incorporate plasmonic metal nanoparticles such as silver and gold into the combined TiO2-SiO2 to fully optimize the TiO2-SiO2's potential in the visible-light region. This article focuses on the challenges in utilizing TiO2 in the visible-light region, the contribution of SiO2 in enhancing photocatalytic activities of the TiO2-SiO2 photocatalyst, and the ability of plasmonic metal nanoparticles (Ag and Au) to edge the TiO2-SiO2 photocatalyst toward an efficient solar photocatalyst.
In this work, fibrous silica-titania (FST) was successfully prepared by the microemulsion method prior to the addition of three types of carbonaceous materials: graphitic-carbon nitride, g-C3N4 (CN), graphene nanoplatelets (GN), and multi-wall carbon nanotubes, MWCNT (CNT), via a solid-state microwave irradiation technique. The catalysts were characterized using XRD, FESEM, TEM, FTIR, UV-Vis DRS, N2 adsorption-desorption, XPS and ESR, while their photoactivity was examined on the degradation of toxic 2-chlorophenol (2-CP). The result demonstrated that the initial reaction rate was in the following order: CNFST (5.1 × 10-3 mM min-1) > GNFST (2.5 × 10-3 mM min-1) > CNTFST (2.3 × 10-3 mM min-1). The best performance was due to the polymeric structure of g-C3N4 with a good dispersion of C and N on the surface FST. This dispersion contributed towards an appropriate quantity of defect sites, as a consequence of the greater interaction between g-C3N4 and the FST support, that led to narrowed of band gap energy (2.98 eV to 2.10 eV). The effect of scavenger and ESR studies confirmed that the photodegradation over CNFST occurred via a Z-scheme mechanism. It is noteworthy that the addition of green carbonaceous materials on the FST markedly enhanced the photodegradation of toxic 2-CP.
We formulated a pH-sensitive chlorhexidine-loaded mesoporous silica nanoparticles (MSN) modified with poly-(lactic-co-glycolic acid) (CHX-loaded/MSN-PLGA) and incorporated into experimental resin-based dentin adhesives at 5 and 10 wt%. Nanocarriers were characterized in terms of morphology, physicochemical features, spectral analyses, drug-release kinetics at varying pH and its effect on dentin-bound proteases was investigated. The modified dentin adhesives were characterized for cytotoxicity, antimicrobial activity, degree of conversion (DC) along with CHX release, micro-tensile bond strength (μTBS) and nano-leakage expression were studied at different pH values and storage time. CHX-loaded/MSN-PLGA nanocarriers exhibited a significant pH-dependent drug release behavior than CHX-loaded/MSN nanocarriers without PLGA modification. The highest percentage of CHX release was seen with 10 wt% CHX-loaded/MSN-PLGA doped adhesive at a pH of 5.0. CHX-loaded/MSN-PLGA modified adhesives exhibited more profound antibiofilm characteristics against S. mutans and more sustained CHX-release which was pH dependent. After 6 months in artificial saliva at varying pH, the 5 wt% CHX-loaded/MSN-PLGA doped adhesive showed excellent bonding under SEM/TEM, higher μTBS, and least nano-leakage expression. The pH-sensitive CHX-loaded/MSN-PLGA could be of crucial advantage for resin-dentin bonding applications especially in reduced pH microenvironment resulting from biofilm formation; and the activation of dentin-bound proteases as a consequence of acid etching and acidic content of bonding resin monomers.
The alkali-silica reaction (ASR) is an important consideration in ensuring the long-term durability of concrete materials, especially for those containing reactive aggregates. Although fly ash (FA) has proven to be useful in preventing ASR expansion, the filler effect and the effect of FA fineness on ASR expansion are not well defined in the present literature. Hence, this study aimed to examine the effects of the filler and fineness of FA on ASR mortar expansion. FAs with two different finenesses were used to substitute ordinary Portland cement (OPC) at 20% by weight of binder. River sand (RS) with the same fineness as the FA was also used to replace OPC at the same rate as FA. The replacement of OPC with RS (an inert material) was carried out to observe the filler effect of FA on ASR. The results showed that FA and RS provided lower ASR expansions compared with the control mortar. Fine and coarse fly ashes in this study had almost the same effectiveness in mitigating the ASR expansion of the mortars. For the filler effect, smaller particles of RS had more influence on the ASR reduction than RS with coarser particles. A significant mitigation of the ASR expansion was obtained by decreasing the OPC content in the mortar mixture through its partial substitution with FA and RS.
Soda lime silica (SLS) waste as the source of silica (SiO2) and ark clamshell (ACS) as the foaming agent has been utilized to fabricate the low-cost and lightweight foam glass-ceramics. A series of 1 and 6 wt% foam glass-ceramics were successfully prepared by the conventional solid-state sintering method at various sintering temperatures for 60 min. The bulk density of the samples has achieved minimum density (1.014 g/cm3) with maximum expansion (62.31%) at 6 wt% of the ACS content sintered at 800 °C for 60 min. The bulk density increases while the linear shrinkage and total porosity decrease with the progression of ACS contents and sintering temperature, where the results correspond with the FESEM micrograph. The result of XRD and FTIR transmittance spectra have shown that the formation of wollastonite crystal has occurred starting at 6 wt% of the ACS content sintered at 800 °C for 30 min. The highest mechanical performance (3.90 MPa) with an average total porosity (8.04%) is observed for the sample containing 1 wt% of ACS. It can be concluded that the composition of foam glass-ceramics (1 and 6 wt%) and sintering temperatures give significant results to the structural, physical, and mechanical properties of the fabricated foam glass-ceramics.
Pretomanid and MCC7433, a novel nitroimidazopyrazinone analog, are promising antitubercular agents that belong to the bicyclic nitroimidazole family. Despite possessing high cell permeability, they suffer from poor aqueous solubility and require specialized formulations in order to be orally bioavailable. To address this limitation, we investigated the use of mesoporous silica nanoparticles (MCM-41) as drug carriers. MCM-41 nanoparticles were synthesized using a sol-gel method, and their surface was further modified with amine and phosphonate groups. A simple rotary evaporation method was used to incorporate the compounds of interest into the nanoparticles, leading to a high encapsulation efficiency of ≥86% with ∼10% loading (w/w). An overall significant improvement of solubility was also observed, and the pharmacological activity of pretomanid and MCC7433 was fully retained when tested in vitro against Mycobacterium tuberculosis using these nanocarriers. Amino-functionalized MCM-41 nanoparticles were found to enhance the systemic exposure of MCC7433 in mice (1.3-fold higher Cmax) compared to MCC7433 alone. The current work highlights the potential of using nanoparticles such as mesoporous silica as a carrier for oral delivery of poorly soluble antibacterial agents against tuberculosis.
In this study, an economic silica based ceramic hollow fiber (HF) microporous membrane was fabricated from guinea cornhusk ash (GCHA). A silica interlayer was coated to form a defect free silica membrane which serves as a support for the formation of thin film composite (TFC) ceramic hollow fiber (HF) membrane for the removal of microplastics (MPs) from aqueous solutions. Polyacrylonitrile (PAN), polyvinyl-chloride (PVC), polyvinylpyrrolidone (PVP) and polymethyl methacrylate (PMMA) are the selected MPs The effects of amine monomer concentration (0.5 wt% and 1 wt%) on the formation of poly (piperazine-amide) layer via interfacial polymerization over the GCHA ceramic support were also investigated. The morphology analysis of TFC GCHA HF membranes revealed the formation of a poly (piperazine-amide) layer with narrow pore arrangement. The pore size of TFC GCHA membrane declined with the formation of poly (piperazine-amide) layer, as evidenced from porosimetry analysis. The increase of amine concentration reduced the porosity and water flux of TFC GCHA HF membranes. During MPs filtration, 1 wt% (piperazine) based TFC GCHA membrane showed a lower transmission percentage of PVP (2.7%) and other suspended MPs also displayed lower transmission. The impact of humic acid and sodium alginate on MPs filtration and seawater pretreatment were also analyzed.
Introduction: Rice husk has portrayed great potential in becoming a sustainable biomass source in producing silica, cellulose and carbon materials, which garnered widespread interest among researchers. The objective of the current study is to determine the morphological and compositional changes in rice husk due to the synergistic effects of ther- mochemical treatment. Methods: Washed and dried rice husk was blended into a fine powder and then subjected to step-wise heat treatment and acid digestion to produce white ash. The intermittent products, as well as the original rice husk and the final ash product, were characterised using analytical instruments to document the morphologi- cal and chemical composition changes. Results: This report highlights the production of pure rice husk ash using a step-wise treatment using a combination of thermochemical treatment and carbonisation. The results showed that a partial breakdown of the lignocellulose components was achieved using directed thermal treatment at low tem- perature. The ionic impurities were leached out in subsequent heated acid treatment. Thereafter, the carbonaceous organic matter was completely converted to carbon during the carbonisation of the sample and the remaining carbon residue was removed during calcination. High purity ash contained agglomerated and nanostructured silica in the dimensions of 20 to 50 nm in the amorphous form. Conclusion: The step-wise treatment allowed systematic removal of each compound while maintaining the amorphous mineral phase of silica and avoiding carbon fixation. Under- standing the effect of each treatment offers insight to produce purer silica from rice husk.
A urea precursor was used for the first time to prepare mesoporous carbon nitride (MCN) by a thermal polymerization process with silica nanospheres as a hard template. Although the prepared MCN samples have similar structures and optical properties, it was revealed that the specific surface area, pore-size distribution, and morphology of the MCN samples depend on the initial mass ratio of urea to silica. Compared to the bulk carbon nitride (BCN) that only gave 20% phenol removal (6 h of irradiation), the activities can be enhanced up to 74% on MCN samples for photocatalytic removal of phenol under visible-light irradiation. The highest conversion was obtained on MCN with an initial mass ratio of urea to silica of 5, which has high surface area of 191 m(2) g(-1) and a nanoporous structure with uniform pore-size distribution of 7 nm. In addition to the high activity, the MCN sample also showed high photocatalytic stability.
Nanoporous materials such as Mobil composite material number 41 (MCM-41) are attractive for applications such as catalysis, adsorption, supports, and carriers. Green synthesis of MCM-41 is particularly appealing because the chemical reagents are useful and valuable. We report on the eco-friendly synthesis of MCM-41 nanoporous materials via multi-cycle approach by re-using the non-reacted reagents in supernatant as mother liquor after separating the solid product. This approach was achieved via minimal requirement of chemical compensation where additional fresh reactants were added into the mother liquor followed by pH adjustment after each cycle of synthesis. The solid product of each successive batch was collected and characterized while the non-reacted reagents in supernatant can be recovered and re-used to produce subsequent cycle of MCM-41. The multi-cycle synthesis is demonstrated up to three times in this research. This approach suggests a low cost and eco-friendly synthesis of nanoporous material since less waste is discarded after the product has been collected, and in addition, product yield can be maintained at the high level.
A study was carried out to investigate correlation between presence of specific microalgal species and Leptoconops biting midge larvae in its breeding habitats. Sand samples containing microalgae were collected from the beach where the midges were most commonly biting and from sand beaches which are potential as breeding habitats of Leptoconops. The survey covered sand beaches from 12 seperate islands. At all sites, the Bacillariophyta constituted the largest representatives of the microalgae community with the majority from the Naviculaceae family. A total of 24 microalgal species were identified from the sand samples collected from the study sites. Sand samples from Kentot Kecil Island had the highest number of algal species (11.0) and the highest algae species diversity ( Shanon-Weiner Diversity Index, H' = 0.884). Besar Island (Johor) had the lowest number of algal species (2.0) whereas Tengol A Island had the lowest algae species diversity (H'=0.234). Highest similarity index was recorded between sand samples collected from Tengol A Island and Tengol B Island (75.0%) followed by Besar Island (Melaka) and Tengol B Island (62.0 %). The variation between other islands were relatively high. Virtually many kinds of algae were found where Leptoconops were breeding but Fragilaria intermedia, Mastigloia minuta and Navicula advena were particularly common.
This study evaluated the use of urethane dimethacrylate (UDMA) as a base monomer to prepare the newly developed flowable composite (FC) using nanohybrid silica derived from rice husk in comparison to bisphenol A-glycidyl methacrylate (Bis-GMA) on the degree of conversion and physicomechanical properties. The different loadings of base monomer to diluent monomer were used at the ratio of 40:60, 50:50, and 60:40. The bonding analysis confirmed the presence of nanohybrid silica in the newly developed FC. Independent t-test revealed a statistically significant increase in the degree of conversion, depth of cure and Vickers hardness of the UDMA-based FC, while surface roughness showed comparable results between the two base monomers. In conclusion, UDMA-based FC demonstrated superior performance with 60%-65% conversions, a significantly higher depth of cure exceeding 1 mm which complies with the Internal Standard of Organization 4049 (ISO 4049), and a substantial increase in Vickers hardness numbers compared to Bis-GMA-based FC, making UDMA a suitable alternative to Bis-GMA as a base monomer in the formulation of this newly developed FC derived from rice husk.
Herein, the polymer nanomatrix of chitosan/SiO2 (CHI/n-SiO2) was enriched with a π-π electron donor-acceptor system using diaromatic rings of benzil (BEZ) assisted via a hydrothermal process to obtain an effective adsorbent of chitosan-benzil/SiO2 (CHI-BEZ/n-SiO2). The polymer nanomatrix (CHI/n-SiO2) and the resulting adsorbent (CHI-BEZ/n-SiO2) were applied to remove the anionic acid red 88 (AR88) dye from aqueous media in a comparative mode. Box-Behnken design (BBD) was adopted to optimize AR88 adsorption onto CHI/n-SiO2 and CHI-BEZ/n-SiO2 with respect to variables that influence AR88 adsorption (adsorbent dose: 0.02-0.1 g/100 mL; pH: 4-10; and time: 10-90). The adsorption studies at equilibrium were conducted with a variety of initial AR88 dye concentrations (20-200 mg/L). The adsorption isotherm results reveal that the AR88 adsorption by CHI/n-SiO2 and CHI-BEZ/n-SiO2 are described by the Langmuir model. The kinetic adsorption profiles of AR88 with CHI/n-SiO2 and CHI-BEZ/n-SiO2 reveal that the pseudo-first-order model provides the best fit results. Interestingly, CHI-BEZ/n-SiO2 has a high adsorption capacity (261.2 mg/g), which exceeds the adsorption capacity of CHI/n-SiO2 (215.1 mg/g) that relates to the surface effects of SiO2 and the functionalization of chitosan with BEZ. These findings show that CHI-BEZ/n-SiO2 represents a highly efficient adsorbent for the removal of harmful pollutants from water, which outperforming the CHI/n-SiO2 system.
Thermoluminescence (TL) properties (radiation sensitivity, dose response, signal fading) of Nd-doped SiO2 optical fibers irradiated with 1.25MeV photons to 1-50Gy were studied. The peak of the glow curve is around 190°C regardless of the dose. The dose response is linear up to 50Gy. The radiation sensitivity is 219nCmg(-1)Gy(-1). The fiber can be a potential candidate for photon radiotherapy dosimetry due to its high radiation sensitivity, linear dose response in a wide range, slow fading, and high spatial resolution due to the small size of the fiber.
Ethanol is a highly combustible chemical universally designed for biomedical applications. In this paper, optical sensing performance of tapered multimode fiber tip coated with carbon nanotube (CNT) thin film towards aqueous ethanol with different concentrations is investigated. The tapered optical multimode fiber tip is coated with CNT using drop-casting technique and is annealed at 70 °C to enhance the binding of the nanomaterial to the silica fiber tip. The optical fiber tip and the CNT sensing layer are micro-characterized using FESEM and Raman spectroscopy techniques. When the developed sensor was exposed to different concentrations of ethanol (5% to 80%), the sensor reflectance reduced proportionally. The developed sensors showed high sensitivity, repeatability and fast responses (<55 s) towards ethanol.
The thermoluminescence (TL) glow curves and kinetics parameters of Thulium (Tm) doped silica cylindrical fibers (CF) are presented. A linear accelerator (LINAC) was used to deliver high-energy radiation of 21MeV electrons and 10MV photons. The CFs were irradiated in the dose range of 0.2-10Gy. The experimental glow curve data was reconstructed by using WinREMS. The WinGCF software was used for the kinetic parameters evaluation. The TL sensitivity of Tm-doped silica CF is about 2 times higher as compared to pure silica CF. Tm-doped silica CF seems to be more sensitive to 21MeV electrons than to 10MV photons. Surprisingly, no supralinearity was displayed and a sub-linear response of Tm-doped silica CF was observed within the analyzed dose range for both 21MeV electrons and 10MV photons. The Tm-doped silica CF glow curve consists of 5 individual glow peaks. The Ea of peak 4 and peak 5 was highly dependent on dose when irradiated with photons. We also noticed that the electron radiation (21MeV) caused a shift of glow peak by 7-13°C to the higher temperature region compared with photons radiation (10MV). Our Tm-doped fibers seem to give high TL response after 21MeV electrons, which gives around 2 times higher peak integral as compared with 10MV photon radiation. We concluded that peak 4 is the first-order kinetic peak and can be used as the main dosimetric peak of Tm-doped silica CF.
This paper aimed to describe the effects of sand mining on the Kelantan River with respect to physical and chemical parameter analyses. Three replicates of water samples were collected from five stations along the Kelantan River (November 2010 until February 2011). The physical parameters included water temperature, water conductivity, dissolved oxygen (DO), pH, total dissolved solids (TDS), total suspended solids (TSS) and turbidity, whereas the chemical parameters included the concentration of nitrogen nutrients such as ammonia, nitrate and nitrite. The Kelantan River case study revealed that TSS, turbidity and nitrate contents exceed the Malaysian Interim National Water Quality Standard (INWQS) range and are significantly different between Station 1 (KK) and Station 3 (TM). Station 1 has the largest variation of TDS, TSS, turbidity and nitrogen nutrients because of sand mining and upstream logging activities. The extremely high content of TSS and the turbidity have caused poor and stressful conditions for the aquatic life in the Kelantan River.
The unique three-dimensional pore structure of KCC-1 has attracted significant attention and has proven to be different compared to other conventional mesoporous silica such as the MCM-41 family, SBA-15, or even MSN nanoparticles. In this research, we carefully examine the morphology of KCC-1 to define more appropriate nomenclature. We also propose a formation mechanism of KCC-1 based on our experimental evidence. Herein, the KCC-1 morphology was interpreted mainly on the basis of compiling all observation and information taken from SEM and TEM images. Further analysis on TEM images was carried out. The gray value intensity profile was derived from TEM images in order to determine the specific pattern of this unique morphology that is found to be clearly different from that of other types of porous spherical-like morphologies. On the basis of these results, the KCC-1 morphology would be more appropriately reclassified as bicontinuous concentric lamellar morphology. Some physical characteristics such as the origin of emulsion, electrical conductivity, and the local structure of water molecules in the KCC-1 emulsion were disclosed to reveal the formation mechanism of KCC-1. The origin of the KCC-1 emulsion was characterized by the observation of the Tyndall effect, conductometry to determine the critical micelle concentration, and Raman spectroscopy. In addition, the morphological evolution study during KCC-1 synthesis completes the portrait of the formation of mesoporous silica KCC-1.
Engineered aluminum oxide (Al2O3), titanium dioxide (TiO2), and silicon dioxide (SiO2) nanoparticles (NPs) are utilized in a broad range of applications; causing noticeable quantities of these materials to be released into the environment. Issues of how and where these particles are distributed into the subsurface aquatic environment remain as major challenges for those in environmental engineering. In this study, transport and retention of Al2O3, TiO2, and SiO2 NPs through various saturated porous media were investigated. Vertical columns were packed with quartz-sand, limestone, and dolomite grains. The NPs were introduced as a pulse suspended in aqueous solutions and breakthrough curves in the column outlet were generated using an ultraviolet-visible spectrophotometer. It was found that Al2O3 and TiO2 NPs are easily transported through limestone and dolomite porous media whereas NPs recoveries were achieved two times higher than those found in the quartz-sand. The highest and lowest SiO2-NPs recoveries were also achieved from the quartz-sand and limestone columns, respectively. The experimental results closely replicated the general trends predicted by the filtration and DLVO calculations. Overall, NPs mobility through a porous medium was found to be strongly dependent on NP surface charge, NP suspension stability against deposition, and porous medium surface charge and roughness.