Synthesis Route Research Articles

The efficacy of nano‐cellulose‐based composites in heavy metal removal from wastewater: a comprehensive review

AbstractThis comprehensive study delves into the innovative application of nano‐cellulose‐based composites for addressing the multifaceted challenges of wastewater treatment. This review introduces the innovative use of nano‐cellulose composites, particularly highlighting the novel synthesis routes that enhance their pollutant adsorption capabilities beyond conventional materials. These materials stand out for their regenerative properties and integration with functionalized matrix materials, marking significant advancements in sustainable wastewater treatment technologies. As the environmental and public health risks associated with untreated wastewater escalate, the development of efficient and sustainable treatment technologies has become crucial. Nano‐cellulose composites, derived from natural and renewable sources, offer significant advantages, including high surface area, superior mechanical strength, and notable biodegradability. This review explores various synthesis methods—mechanical, chemical, and enzymatic—that enhance the adaptability of nano‐cellulose composites to meet specific treatment needs. Main findings demonstrate these composites' effectiveness in removing a wide array of pollutants, including heavy metals, organic compounds, dyes, and microbial contaminants, with detailed removal capacities provided for each pollutant category in comparative tables. The potential for regeneration and reuse highlights their practical sustainability and economic viability. Future research should focus on improving production scalability and cost‐effectiveness, assessing environmental impacts and ensuring regulatory compliance to advance the application of nano‐cellulose composites in wastewater treatment. This study paves the way for these materials to become central to innovative, efficient, and eco‐friendly wastewater management strategies. © 2024 Society of Chemical Industry (SCI).

Research Progress in the Synthesis of N-Acyl Amino Acid Surfactants: A Review

This paper reviews the research progress in the synthesis of N-acyl amino acid surfactants, including chemical synthesis methods, enzymatic synthesis methods, chemo-enzymatic methods, and fermentation methods. Chemical synthesis is currently the main route for laboratory and industrial synthesis, including methods such as direct dehydration condensation of fatty acids, amidation of fatty acid anhydrides, carbonyl addition of fatty amides, amidation of fatty acid activated esters, amidation of fatty acid methyl esters, amidation of oils and fats, hydrolysis of fatty nitriles, and Schotten–Baumann condensation. Enzymatic synthesis has the advantages of mild reaction conditions and being green and pollution-free, but the yield is relatively low. The chemo-enzymatic method combines the advantages of enzymatic and chemical methods, but it has not been widely promoted. Fermentation methods have low production costs and are environmentally friendly but the technology is not yet mature. This paper elaborates on the principles, advantages, and disadvantages of each synthesis method and provides an outlook on future research directions.

Review on the synthesis routes of nickel manganite – a potential material for thermistor applications

Review on the synthesis routes of nickel manganite – a potential material for thermistor applications

Novel Top-Down Synthesis of Covalent Organic Frameworks for Uranyl Ion Capture.

Seeking novel synthetic methodology to further promote the preparation of covalent organic frameworks (COFs) has long been our pursuit but remains a challenging task. Herein, we report a new protocol, a top-down approach for facile synthesis of COFs. Interestingly, our top-down route can impressively generate extended COFs by reticular chemistry which cannot be accessed by the commonly used bottom-up synthesis route. Notably, our top-down method also has outstanding advantages in achieving what we are pursuing in COFs, such as heteropores and multiple components. The current findings not only dramatically reduce the difficulty of COF synthesis but also are generally applicable for the synthesis of complicated COFs constructed from different building blocks and linkages.

Development of an improved and facile synthesis route of the FGFR inhibitor erdafitinib

Development of an improved and facile synthesis route of the FGFR inhibitor erdafitinib

Multilayer-coating process for the synthesis of nickel-silicate composite with high Ni loading as high-rate performance lithium-ion anode material

BackgroundMetal silicates possess several important advantages as electrode materials for lithium-ion batteries (LIBs), including straightforward synthesis, low cost, and high thermal stability. A green synthesis routes that are capable of increasing metal loading and reducing the impact on the environment are required. MethodsA Ni-silicate with a multilayer structure and a Ni/Si molar ratio of 0.25 is first prepared using the co-precipitation method. The as-synthesized product is then repeatedly immersed in a Ni2+ solution to obtain Ni-silicate with the desired Ni contents (Ni/Si molar ratio: 0.50–2.00). Finally, the resulting Ni-silicate is reconstructed by hydrothermal treatment under various temperatures (70 °C, 100 °C, 150 °C) and durations (3 h and 24 h) to obtain Ni-phyllosilicate. The effects of the hydrothermal treatment temperature, hydrothermal time, and Ni/Si ratio on the structure, morphology, and surface area of the Ni-silicate composites are examined. Significant FindingsThe Ni-silicate with a Ni/Si ratio of 1.5 has a reversible capacity of 729 mAhg-1, which exceeds traditional graphite anodes (372 mAhg-1). Furthermore, the material exhibits a capacity retention of up to 80 % as the current density is increased from 0.025 Ag-1 to 0.5 Ag-1. Thus, the synthesized Ni-silicate composite is a promising candidate material for LIB anode.

Lithium iodide promoted CO2 hydrogenation towards ethanol via biphasic lewis-acid-base pairs synergistic catalysis

Ethanol synthesis via CO2 hydrogenation is of great importance in view of its high-value utilization. Herein, combining with heterogeneous and homogenous catalysis, we have developed an efficient biphasic Lewis-acid-base pairs synergistic catalysis strategy from CO2 hydrogenation. Apart from conventional heterogeneous ethanol synthesis route, it was surprisingly found that LiI homogenous promoter significantly enhanced CO2 conversion, ethanol selectivity, and productivity. LiI promoted CO2 dissolution in pure water and accelerated reaction intermediates consumption, favoring CO2 conversion. In detail, it can weaken C-O bond of CH3OH intermediate through Li+-I- Lewis-acid-base catalysis. The formed CH3I* with lower bond energy for C-I was more facile to dissociate into CH3*, favoring its subsequent coupling with CO* to form ethanol. In combination of Rh1/CeTiOx catalyst, LiI promoter, and methanol as solvent, a record-breaking ethanol yield was achieved (223.1 mmol·g−1·h−1). The obtained ethanol yield was about 18.7 times of that reported the best result in literatures. Especially, the established catalyst system could also be applied for synthesis of higher-carbon-number alcohols by the CO2 hydrogenation with other alcohols solvent (CnH2n+1OH, n = 2,3…).

Wormhole Mesoporous Silica Framework with Enhanced Thiol Loading for Improved Hg2+ Sequestration.

Thiol-functionalized mesoporous silica and materials potentially dedicated to diverse applications of composite materials, metal colloids, and metal catalysts, etc. Here, we developed a new synthesis route for 3-methacryloxypropyl trimethoxy silane (MPTMS) functionalized mesoporous silica (KIT-6), achieving a 71.5 % enhancement in thiol functionalization on KIT-6 surfaces. Characterization using XRD, TEM, BET, FTIR, Raman, 29Si NMR, XPS, and ICP-OES revealed structural and morphological features. XRD, TEM, and BET confirmed the three-dimensional structural stabilization of mesoporous silica with ~4 nm pore diameter and a surface area of 1451 m2 g-1. FTIR, Raman, and 29Si NMR studies established the mechanism of thiol functionalization, the formation of a new wormhole chain structural framework (WCSF), and stabilization through hydrogen bonding within the mesopores. The 29Si NMR spectra showed characteristic peaks (T3, T2, Q4, Q3) indicating self-condensed functionalized thiols with siloxane networks. XPS analysis validated enhanced thiol functionalization, indicating a structurally homogeneous WCSF suitable for mercury adsorption. ICP-OES measured a mercury adsorption capacity of 3199.6 mg g-1 for KIT-6, with an Hg2+/S ratio of 1.8, corroborated by molecular structure and mechanism analysis. This innovative thiol functionalization approach enhances the efficacy of applications such as extracting Hg2+ from contaminated sources.

Mechanochemical Synthesis of Carbazole Isomer Phosphors.

The 1H-benzo[f]indole (Bd[f]), a carbazole (Cz) isomer is first reported as the source of Cz-based phosphors in 2020. In this work, the novel carbazole isomers, 1H-benzo[g]indole (Bd[g]) based derivatives, are synthesized by a one-step solvent-free mechanical ball milling reaction, establishing a facile, efficient, and environmentally friendly method for the synthesis of new Cz isomer phosphorescent derivatives with high yields compared to previously reported multi-step solvent-based thermochemical synthesis routes of Bd[f] derivatives with low yields. Six Bd[g] derivatives with different substituents, namely OCH3-Bd, In-Bd, Bn-Bd, F-Bd, Cl-Bd, and Br-Bd, are synthesized, which exhibit distinctly different single-crystal structures and phosphorescent properties. After irradiation with 365nm UV light, Bd[g] derivatives-doped poly (methyl methacrylate) (PMMA) films exhibit photoactivated green room-temperature phosphorescence with ultra-long lifetimes up to 1.65s. Interestingly, the phosphorescence is stable in seawater along with good bactericidal properties, which also provide new candidates for indole-based marine antifoulants. This study demonstrates that mechanical ball milling is an efficient method for the synthesis of benzoindole heterocycles. Bd[g], as new members of the benzoindole family, are new building units to construct carbazole isomer phosphorescent molecules besides Bd[f].

Production of L-lactic acid from methanol by engineered yeast Pichia pastoris

Lactic acid (LA) serves as a widely used platform compound and has received significant attention as a raw material for synthesis of biodegradable polylactic acid. Currently, LA is mainly produced through microbial fermentation, but its high costs undermine its competitive advantage against other materials, necessitating the development of novel production routes. Methanol bioconversion represents an emerging low-carbon circular economy, where LA could become an outstanding representative product. This study successfully established an efficient methanol-based LA synthesis route in Pichia pastoris. Through systematic metabolic engineering strategies, including screening lactate dehydrogenase, modification of cofactor preference, blocking LA consumption pathway, and mitochondrial LA synthesis compartmentalization, 4.2 g/L L-LA was produced in fed-batch fermentation by using methanol as the sole carbon source. Through multi-dimensional and spatial engineering of enzyme, a cell factory was developed for efficient synthesis of L-LA, highlights the significant potential of the low-carbon synthesis route for L-LA via methanol bioconversion.

A general flame aerosol route to kinetically stabilized metal-organic frameworks

Metal-organic frameworks (MOFs) are highly attractive porous materials with applications spanning the fields of chemistry, physics, biology, and engineering. Their exceptional porosity and structural flexibility have led to widespread use in catalysis, separation, biomedicine, and electrochemistry. Currently, most MOFs are synthesized under equilibrium liquid-phase reaction conditions. Here we show a general and versatile non-equilibrium flame aerosol synthesis of MOFs, in which rapid kinetics of MOF formation yields two distinct classes of MOFs, nano-crystalline MOFs and amorphous MOFs. A key advantage of this far-from-equilibrium synthesis is integration of different metal cations within a single MOF phase, even when this is thermodynamically unfavorable. This can, for example, produce single-atom catalysts and bimetallic MOFs of arbitrary metal pairs. Moreover, we demonstrate that dopant metals (e.g., Pt, Pd) can be exsolved from the MOF framework by reduction, forming nanoclusters anchored on the MOF. A prototypical example of such a material exhibited outstanding performance as a CO oxidation catalyst. This general synthesis route opens new opportunities in MOF design and applications across diverse fields and is inherently scalable for continuous production at industrial scales.

Optimisation, Synthesis, and Characterisation of ZnO Nanoparticles Using Leonotis ocymifolia (L. ocymifolia) Leaf Extracts for Antibacterial and Photodegradation Applications

This work presents a green synthesis route, which utilises extracts from an indigenous plant in South Africa, eastern and southern Africa that is understudied and underutilised, for preparing zinc oxide nanoparticles (ZnO NPs). This study involved optimisation of the green synthesis method using Leonotis ocymifolia (L.O.) extracts and performing comparative studies on the effects of using different zinc (Zn) salt precursors; zinc sulphate heptahydrate (Z001) and zinc acetate dihydrate (Z002) to synthesise the ZnO NPs. The comparative studies also compared the L.O-mediated ZnO NPs and chemical-mediated ZnO NPs (Z003). The as-prepared ZnO NPs were tested for their effectiveness in the photodegradation of methylene blue (MB) dye. Furthermore, antibacterial studies were conducted using the agar well diffusion method on Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) bacteria. The structural, morphological, and optical characteristics of the synthesised ZnO NPs were analysed using XRD, FTIR, SEM, EDS, DRS, and BET techniques. The XRD results indicated that the L.O-mediated ZnO NPs had smaller crystallite sizes (18.24–19.32 nm) than their chemically synthesised counterparts (21.50 nm). FTIR confirmed the presence of biomolecules on the surface of the L.O-mediated NPs, and DRS analysis revealed bandgap energies between 3.07 and 3.18 eV. The EDS results confirmed the chemical composition of the synthesised ZnO NPs, which were made up of Zn and O atoms. Photocatalytic studies demonstrated that the L.O-mediated ZnO NPs (Z001) exhibited a superior degradation efficiency of the MB dye (89.81%) compared to chemically synthesised ZnO NPs (56.13%) under ultraviolet (UV) light for 240 min. Antibacterial tests showed that L.O-mediated ZnO NPs were more effective against S. aureus than E. coli. The enhanced photocatalytic and antibacterial properties of L.O-mediated ZnO NPs highlight their potential for environmental remediation and antimicrobial applications, thus supporting sustainable development goals.

Total Synthesis Analysis of Pseuboyenes D

In this work, we propose a total synthesis route for the antifungal agent Pseuboyenes D, a compound derived from Pseudallescheria boydii CS-793. Pseuboyenes D exhibits antifungal activity comparable to Amphotericin B while offering the advantage of a simpler structure, making it a promising candidate for clinical applications. The system became the focus of this analysis due to its regioselectivity, and after exploration, a [2+2] photocycloaddition and ring expansion strategy was adopted to construct the key bridged ring system. The route employs readily available substrates and mild reaction conditions, making it scalable and suitable for large-scale production. Computational analysis of the regioselectivity of the photocycloaddition revealed that the bridged adduct was thermodynamically favored over the fused system. The synthetic route was further diversified by incorporating functional group modifications using TMS derivatives, enhancing the potential for pharmacological applications. Overall, this work establishes an efficient and scalable synthetic pathway for Pseuboyenes D, paving the way for future applications in antifungal drug development.

Growth Kinetics of Graphene on Cu(111) Foils from Methane, Ethyne, Ethylene, and Ethane

AbstractChemical vapor deposition of carbon precursors on Cu‐based substrates at temperatures exceeding 1000 °C is currently a typical route for the scalable synthesis of large‐area high‐quality single‐layer graphene (SLG) films. Using molecules with higher activities than CH4 may afford lower growth temperatures that might yield fold‐ and wrinkle‐free graphene. The kinetics of growth of graphene using hydrocarbons other than CH4 are of interest to the scientific and industrial communities. We measured the growth rates of graphene islands on Cu(111) foils by using C2H2, C2H4, C2H6 and CH4, respectively (each mixed with H2). From such kinetics data we obtain the activation enthalpy (ΔH≠) of graphene growth as shown in parentheses (C2H2 (0.93±0.09 eV); C2H4 (2.05±0.19 eV); C2H6 (2.50±0.11 eV); CH4 (4.59±0.26 eV)); C2Hy (y=2, 4, 6) show similar growth behavior but CH4 is different. Computational fluid dynamics and density functional theory simulations suggest that C2Hy differs from CH4 due to different values of adsorption energy and the lifetime of relevant carbon precursors on the Cu(111) surface. Combining experimental and simulation results, we find that the rate determining step (RDS) is the dissociation of the first C−H bond of CH4 molecules in the gas phase, while the RDS using C2Hy is the first dehydrogenation of adsorbed C2Hy that happens with assistance of H atoms adsorbed on the Cu(111) surface. By using C2H2 as the carbon precursor, high‐quality single‐crystal adlayer‐free SLG films are achieved on Cu(111) foils at 900 °C.

Growth Kinetics of Graphene on Cu(111) Foils from Methane, Ethyne, Ethylene, and Ethane.

Chemical vapor deposition of carbon precursors on Cu-based substrates at temperatures exceeding 1000 °C is currently a typical route for the scalable synthesis of large-area high-quality single-layer graphene (SLG) films. Using molecules with higher activities than CH4 may afford lower growth temperatures that might yield fold- and wrinkle-free graphene. The kinetics of growth of graphene using hydrocarbons other than CH4 are of interest to the scientific and industrial communities. We measured the growth rates of graphene islands on Cu(111) foils by using C2H2, C2H4, C2H6 and CH4, respectively (each mixed with H2). From such kinetics data we obtain the activation enthalpy (ΔH≠) of graphene growth as shown in parentheses (C2H2 (0.93±0.09 eV); C2H4 (2.05±0.19 eV); C2H6 (2.50±0.11 eV); CH4 (4.59±0.26 eV)); C2Hy (y=2, 4, 6) show similar growth behavior but CH4 is different. Computational fluid dynamics and density functional theory simulations suggest that C2Hy differs from CH4 due to different values of adsorption energy and the lifetime of relevant carbon precursors on the Cu(111) surface. Combining experimental and simulation results, we find that the rate determining step (RDS) is the dissociation of the first C-H bond of CH4 molecules in the gas phase, while the RDS using C2Hy is the first dehydrogenation of adsorbed C2Hy that happens with assistance of H atoms adsorbed on the Cu(111) surface. By using C2H2 as the carbon precursor, high-quality single-crystal adlayer-free SLG films are achieved on Cu(111) foils at 900 °C.

A Novel Synthesis Route of Phenyl Quinoline from Nitrochalcone with Hydrazine Hydrate in the Presence of Pd/C

Quinoline is widely known to have many biological activities. Therefore, the development of the synthesis method of a quinoline derivative framework is a priority. A phenyl quinoline derivative, 6,7-dimethoxy-2-phenylquinoline Q1, has been successfully synthesized via a novel one-pot reaction that involves reduction, cyclization, and followed by dehydration of nitrochalcone derivate, 3-(4,5-dimethoxy-2-nitrophenyl)-1-phenylprop-2-en-1-one C1. The reaction was carried out using 80 % hydrazine hydrate in the presence of 10% Pd/C as a catalyst in an ethanol medium. Target compound Q1 was afforded in a good yield of 69.18% in a relatively short reaction time of ±2 h.

Order evolution from a high‐entropy matrix: Understanding and predicting paths to low‐temperature equilibrium

AbstractInterest in high‐entropy inorganic compounds originates from their ability to stabilize cations and anions in local environments that rarely occur at standard temperature and pressure. This leads to new crystalline phases in many‐cation formulations with structures and properties that depart from conventional trends. The highest‐entropy homogeneous and random solid solution is a parent structure from which a continuum of lower‐entropy offspring can originate by adopting chemical and/or structural order. This report demonstrates how synthesis conditions, thermal history, and elastic and chemical boundary conditions conspire to regulate this process in Mg0.2Co0.2Ni0.2Cu0.2Zn0.2O, during which coherent CuO nanotweeds and spinel nanocuboids evolve. We do so by combining structured synthesis routes, atomic‐resolution microscopy and spectroscopy, density functional theory, and a phase field modeling framework that accurately predicts the emergent structure and local chemistry. This establishes a framework to appreciate, understand, and predict the macrostate spectrum available to a high‐entropy system that is critical to rationalizing property engineering opportunities.

Charge Transfer Induced Phase Transition in Li2MnO3at High Pressure.

Efficient and better energy storage materials are of utmost technological importance to reduce energy dependence on the fossil fuels. Li2MnO3is one such material having potential to meet most of the requirements for energy storage. This material has been synthesized using solid state synthesis route. High pressure structural and vibrational studies on this material have been carried out upto~ 22 and 26 GPa respectively. These investigations show occurrence of a hitherto unknown second order phase transition to a new low symmetry phase whose symmetry is constrained to be monoclinic with space group P21/n at pressure of ~ 2.3 GPa in Li2MnO3. The bulk modulus and its derivative determined by fitting the P-V data with third order Birch-Murnaghan (B-M) equation of state (EOS) are 113.3 ± 13.1 GPa and 4.1 ± 1.2 respectively. Mode Grüneisen parameter calculated for all the Raman modes show positive values which indicates the absence of any soft mode in this material. A microscopic mechanism based on bond-charge transfer is invoked and applied to understand the spectroscopic changes occurring in this material which also manifests second order structural phase transition. Enhancement in covalent character of Li-O bonds in the Li-O polyhedra is inferred based on the spectroscopic observation and above mechanism.&#xD.

Determination of the particle size distribution of cube-shaped colloidal perovskite quantum dots from photoluminescence spectra: A combined theoretical-experimental approach.

A theoretical-experimental approach is proposed to convert the photoluminescence spectra of colloidal perovskite quantum dot ensembles into accurate estimates for their intrinsic particle size distribution functions. Two main problems were addressed and properly correlated: the size dependence of the first excitonic transition in a single cube-shaped quantum dot and the inhomogeneous broadening of the fluorescence line shape due to the size nonuniformity of the chemically prepared quantum dot suspension in addition to the single-dot homogeneous broadening. By applying the reported methodology to CsPbBr3 quantum dot samples belonging to the strong and intermediate confinement regimes, the calculated size distributions exhibited close agreement with those obtained from transmission electron microscopy, with precise estimates for the average particle size and standard deviation. Specifically for strongly confined ultrasmall CsPbBr3 quantum dots, the presented spectroscopic model for size distribution computation is based on a new analytical expression for the size-dependent bandgap, which was developed within the framework of the finite-depth square-well effective mass approximation accounting for band nonparabolicity effects. Such a quantum mechanical approach correctly predicts the expected transition to the intermediate confinement regime in sufficiently large quantum dots, which are traditionally described by the well-known bandgap equation in the infinite potential barrier limit with a spatially correlated electron-hole wavefunction and nonparabolic carrier effective masses. The proposed calculation scheme originates from general theoretical considerations so that it can be readily adapted to semiconductor quantum dots of many other systems, from all inorganic metal halides to hybrid perovskite materials, regardless of the adopted chemical synthesis route.

Interplay between de novo and salvage pathways of GDP-fucose synthesis

GDP-fucose is synthesised via two pathways: de novo and salvage. The first uses GDP-mannose as a substrate, and the second uses free fucose. To date, these pathways have been considered to work separately and not to have an influence on each other. We report the mutual response of the de novo and salvage pathways to the lack of enzymes from a particular route of GDP-fucose synthesis. We detected different efficiencies of GDP-fucose and fucosylated structure synthesis after a single inactivation of enzymes of the de novo pathway. Our study demonstrated the unequal influence of the salvage enzymes on the production of GDP-fucose by enzymes of the de novo biosynthesis pathway. Simultaneously, we detected an elevated level of one of the enzymes of the de novo pathway in the cell line lacking the enzyme of the salvage biosynthesis pathway. Additionally, we identified dissimilarities in fucose uptake between cells lacking TSTA3 and GMDS proteins.