Continuous sonochemical nanotransformation of lignin - Process design and control.

As the most abundant renewable aromatic polymer on the planet, lignin is gaining growing interest in replacing petroleum-based chemicals and products. However, only <5 % of industrial lignin waste is revalorized in its macromolecular form as additives, stabilizing agents or dispersant and surfactants. Herein, revalorization of this biomass was achieved by implementing an environmentally-friendly continuous sonochemical nanotransformation to obtain highly concentrated lignin nanoparticles (LigNPs) dispersions for added-value material applications. With the aim to further model and control a large-scale ultrasound-assisted lignin nanotransformation, a two-level factorial design of experiment (DoE) was implemented varying the ultrasound (US) amplitude, flow rate, and lignin concentration. Size and polydispersity measurements together with the UV-Vis spectra of lignin recorded at different time intervals of sonication allowed to monitor and understand the sonochemical process on a molecular level. The light scattering profile of sonicated lignin dispersions showed a significant particle size reduction in the first 20 min, followed by moderate particle size decrease below 700 nm until the end of the 2 h process. The response surface analysis (RSA) of the particle size data revealed that the lignin concentration and sonication time were the most important factors to achieve smaller NPs. From a mechanistic point of view, a strong impact of the particle-particle collisions due to sonication seems to be responsible for the decrease in particle size and homogenization of the particle distribution. Unexpectedly, a strong interaction between the flow rate and US amplitude on the particle size and nanotransformation efficiency was observed, yielding smaller LigNPs at high amplitude and low flow rate or vice versa. The data derived from the DoE were used to model and predict the size and polydispersity of the sonicated lignin. Furthermore, the use of the NPs spectral process trajectories calculated from the UV-Vis spectra showed similar RSA model as the dynamic light scattering (DLS) data and will potentially allow the in-line monitoring of the nanotransformation process.

Exploring the untapped catalytic application of a ZnO/CuI/PPy nanocomposite for the green synthesis of biologically active 2,4,5-trisubstituted imidazole scaffolds.

This work is focused on designing an innovative, efficient, and reusable heterogeneous ZnO/CuI/PPy nanocomposite via the self-assembly approach where pyrrole is oxidized into polypyrrole (PPy) and pyrrole also behaves as a reductant in the presence of KI. This so-obtained material was characterized by XRD, FTIR, FESEM, EDX, TEM, XPS, and ICP. TEM clearly shows a spherical morphology with the particle size ranging between 18 and 42 nm. The fabricated nanomaterial was tested for one-pot catalytic synthesis of biologically active 2,4,5-trisubstituted imidazoles under solvent-free conditions. The present work includes the benefits of an easy work-up procedure, higher product yield, shorter reaction duration, and no additional additive requirement under green and sustainable conditions. Moreover, the catalyst exhibited reusability for six runs with no considerable reduction in the respective yields and reactivity (confirmed by XRD, SEM, and TEM of the recycled catalyst). The ICP study shows very low leaching of copper (2.08 ppm) and zinc (0.12 ppm) metals. The approach also presented better values of green metrics like the E-factor, process mass intensity, carbon efficiency and reaction mass efficiency.

An efficient approach for the green synthesis of biologically active 2,3-dihydroquinazolin-4(1H)-ones using a magnetic EDTA coated copper based nanocomposite.

2,3-Dihydroquinazolinone derivatives are known for antiviral, antimicrobial, analgesic, anti-inflammatory, and anticancer activities. However, recent approaches used for their synthesis suffer from various drawbacks. Therefore, we have fabricated a highly efficient magnetic EDTA-coated catalyst, Fe3O4@EDTA/CuI via a simple approach. The ethylenediamine tetraacetic acid (EDTA) plays a crucial role by strongly trapping the catalytic sites of CuI nanoparticles on the surface of the Fe3O4 core. The designed nanocatalyst demonstrates its potential for the catalytic synthesis of 2,3-dihydroquinazolinones using 2-aminobenzamide with aldehydes as the reaction partners. The nanocatalyst was thoroughly characterized through X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), vibrating sample magnetometry (VSM), transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma analysis (ICP). The physiochemically characterized nanocatalyst was tested for synthesis of 2,3-dihydroquinazolinones and higher yields of derivatives were obtained with less time duration. Moreover, the catalytic synthesis is easy to operate without the use of any kind of additives/bases. Furthermore, the catalyst was magnetically recoverable after the completion of the reaction and displayed reusability for six successive rounds without any loss in its catalytic efficiency (confirmed by XRD, SEM, and TEM of the recycled material) along with very low leaching of copper (2.12 ppm) and iron (0.06 ppm) ions. Also, the green metrics were found in correlation with the ideal values (such as E factor (0.10), process mass intensity (1.10), carbon efficiency (96%) and reaction mass efficiency (90.62%)).

Al2O3/CuI/PANI nanocomposite catalyzed green synthesis of biologically active 2-substituted benzimidazole derivatives.

This work is generally focused on the synthesis of an efficient, reusable and novel heterogeneous Al2O3/CuI/PANI nanocatalyst, which has been well synthesized by a simple self-assembly approach where aniline is oxidized into PANI and aniline in the presence of KI also acts as a reductant. The nanocatalyst was well characterized by XRD, FTIR, SEM, EDX, TEM, BET and XPS techniques. In this study, the fabricated material was employed for the catalytic one-pot synthesis of 2-substituted benzimidazoles via condensation between o-phenylenediamine and aldehydes in ethanol as a green solvent. The present method is facile and offers several advantages such as high % yield, less reaction time, and no use of additive/bases. Also, the catalyst showed better values of green metrics including low E-factor: 0.17, high reaction mass efficiency: 85.34%, high carbon efficiency: 94%, and high process mass intensity: 1.17.

Fabrication of a Gold-Supported NiAlTi-Layered Double Hydroxide Nanocatalyst for Organic Transformations.

This work is mainly focused on the synthesis of an efficient and reusable heterogeneous Au/NiAlTi layered double hydroxide (LDH) nanocatalyst and its applications in the preparation of biologically important xanthene, 1,4-dihydropyridine, polyhydroquinoline, and 4H-pyran derivatives. NiAlTi LDH was designed hydrothermally and then gold was supported over the surface of LDH by using ion-exchange and NaBH4 reduction methods. The synthesized nanocatalyst was physicochemically characterized by X-ray diffractrometry, Fourier-transform infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy, and transmission electron microscopy (TEM). The TEM images confirmed the support of gold nanoparticles over the surface of LDH with a size distribution of 7-9 nm. The well-characterized nanocatalyst was tested for the synthesis of biologically important xanthene, 1,4-dihydropyridine, polyhydroquinoline, and 4H-pyran derivatives. The advantages obtained were excellent yields in a lesser reaction time. Stability and reusability were also accessed; the catalyst was stable even after five cycles. High catalytic efficiency, easy fabrication, and recycling ability of Au/NiAlTi LDH make it a potential catalyst for the synthesis of xanthene, 1,4-dihydropyridine, polyhydroquinoline, and 4H-pyran derivatives.

Calcined Layered Double Hydroxides: Catalysts for Xanthene, 1,4-Dihydropyridine, and Polyhydroquinoline Derivative Synthesis.

This work is generally focused on the synthesis of NiFeTi-layered double hydroxides (LDHs) using a hydrothermal route, which were calcined at various temperatures (varying from 200 to 600 °C). The synthesized materials were physicochemically characterized. X-ray diffraction results revealed the loss of the layered structure on calcination resulting in the formation of layered double oxides (LDOs) or mixed metal oxides, which was also supported by Fourier transform infrared studies. Scanning electron microscopy results also show loss of the layered structure and the creation of LDOs on increasing the temperature. These LDOs were tested as the catalysts for the synthesis of biologically significant xanthene, 1,4-dihydropyridine, and polyhydroquinoline derivatives. Among all, NiFeTi LDH calcined at 600 °C proved to be the best catalyst for the synthesis of these derivative compounds under optimized conditions. The advantages obtained were excellent yields in a lesser reaction time. Stability and reusability were also assessed; the catalyst was stable even after five cycles. Furthermore, the memory effect of the obtained NiFeTi CLDH calcined at 600 °C confirms that the material so formed is a calcined state of LDH itself. High catalytic efficiency, easy fabrication, and recycling ability of NiFeTi CLDH calcined at 600 °C make it a potential catalyst for the synthesis of xanthene, 1,4-dihydropyridine, and polyhydroquinoline derivatives.

Privileged Scaffold Chalcone: Synthesis, Characterization and Its Mechanistic Interaction Studies with BSA Employing Spectroscopic and Chemoinformatics Approaches.

Chalcone, a privileged structure, is considered as an effective template in the field of medicinal chemistry for potent drug discovery. In the present study, a privileged template chalcone was designed, synthesized, and characterized by various spectroscopic techniques (NMR, high-resolution mass spectrometry, Fourier transform infrared (FT-IR) spectroscopy, UV spectroscopy, and single-crystal X-ray diffraction). The mechanism of binding of chalcone with bovine serum albumin (BSA) was determined by multispectroscopic techniques and computational methods. Steady-state fluorescence spectroscopy suggests that the intrinsic fluorescence of BSA was quenched upon the addition of chalcone by the combined dynamic and static quenching mechanism. Time-resolved spectroscopy confirms complex formation. FT-IR and circular dichroism spectroscopy suggested the presence of chalcone in the BSA molecule microenvironment and also the possibility of rearrangement of the native structure of BSA. Moreover, molecular docking studies confirm the moderate binding of chalcone with BSA and the molecular dynamics simulation analysis shows the stability of the BSA-drug complex system with minimal deformability fluctuations and potential interaction by the covariance matrix. Moreover, pharmacodynamics and pharmacological analysis show good results through Lipinski rules, with no toxicity profile and high gastrointestinal absorptions by boiled egg permeation assays. This study elucidates the mechanistic profile of the privileged chalcone scaffold to be used in therapeutic applications.

Simultaneous Elimination of Dyes and Antibiotic with a Hydrothermally Generated NiAlTi Layered Double Hydroxide Adsorbent.

In this study, a hydrothermal route was used to design a novel NiAlTi layered double hydroxide. The material so-obtained was characterized using various physiochemical techniques such as X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetric analysis for structural analysis, scanning electron microscopy, transmission electron microscopy for morphological analysis, and so on. The material so-obtained was further applied for wastewater remediation and was found to be an efficient, cost-effective, and reusable adsorbent. Organic contaminants such as dyes and antibiotics were used as pollutants to carry out the removal study. NiAlTi LDH was found to be an excellent adsorbent for the removal of anionic dyes and antibiotics. Excellent performance was shown by NiAlTi LDH at a broad pH range from 4 to 10 for anionic dyes (orange II and methyl orange), but tetracycline removal was predominantly maximum at pH = 9. Further, the kinetic studies also revealed that the adsorption process of both organic contaminants obeyed a pseudo-second-order model. In addition, the Langmuir isotherm adsorption model fitted the experimental results for both types of pollutants very well. The attained maximum adsorption capacity was superb for both organic dyes and antibiotics (1250 mg/g for MO, 2000 mg/g for OII, and 238.09 mg/g for TC). NiAlTi LDH was also capable of simultaneous elimination from a mixture of antibiotics and dyes. Further, NiAlTi LDH also showed outstanding stability and reusability, making it one of the most promising materials for large-scale wastewater remediation contaminated by dyes and antibiotics.

MoS4 2- intercalated NiFeTi LDH as an efficient and selective adsorbent for elimination of heavy metals.

The enormous increase of heavy metal pollution has led to a rise in demand for synthesizing efficient and stable adsorbents for its treatment. Therefore, we have designed a novel adsorbent by introducing (MoS4)2- moieties within the layers of NiFeTi LDH-NO3, via an ion exchange mechanism, as a stable and efficient adsorbent to deal with the increasing water pollution due to heavy metals. Characterization techniques such as XRD, FTIR, TGA, SEM, TEM, and Raman spectroscopy were used to confirm the formation of (MoS4)2- intercalated NiFeTi LDH and structural changes after the adsorption process. The efficiency of the material was tested with six heavy metal ions, among which it was found to be effective for toxic Pb2+ and Ag+ ions. When selectivity was studied with all six of the metal ions copresent in one solution, the material showed greater selectivity for Pb2+ and Ag+ ions with the selectivity order of Ni2+ < Cu2+ < Zn2+ < Fe3+ < Pb2+ < Ag+, with great adsorption capacities of 653 mg g-1 for Pb2+ and 856 mg g-1 for Ag+ metal ions. Further, the kinetics adsorption study for both the metal ions had a great correlation with the pseudo-second-order model and supported the chemisorption process via the formation of M-S bonding. The adsorption process obeyed the Langmuir model. Therefore, the MoS4-LDH material could be a promising adsorbent for the removal of heavy metals.

Recent advancements in synthetic methodologies of 3-substituted phthalides and their application in the total synthesis of biologically active natural products.

We have provided a critical review that focuses on key developments in the area of 3-substituted phthalides and their role in the development of important biologically active natural products. 3-Substituted phthalides are vital molecules owing to their fascinating biological activity. The scope, isolation, and characterization of various naturally occurring racemic and chiral 3-substituted phthalides have been covered. We have put significant emphasis on recently developed research methodologies for the synthesis of racemic and chiral 3-substituted phthalides. These newer approaches are essential for the development of newer and elegant strategies for the synthesis of phthalide-based or similar molecular architecture with broader substrate scope and higher stereoselectivities. Also, we have discussed the application of 3-substituted phthalides as a precursor for the synthesis of natural products and their analogs.

A new biocompatible ternary Layered Double Hydroxide Adsorbent for ultrafast removal of anionic organic dyes.

It would be of great significance to introduce a new biocompatible Layered Double Hydroxide (LDH) for the efficient remediation of wastewater. Herein, we designed a facile, biocompatible and environmental friendly layered double hydroxide (LDH) of NiFeTi for the very first time by the hydrothermal route. The materialization of NiFeTi LDH was confirmed by FTIR, XRD and Raman studies. BET results revealed the high surface area (106 m2/g) and the morphological studies (FESEM and TEM) portrayed the sheets-like structure of NiFeTi nanoparticles. The material so obtained was employed as an efficient adsorbent for the removal of organic dyes from synthetic waste water. The dye removal study showed >96% efficiency for the removal of methyl orange, congo red, methyl blue and orange G, which revealed the superiority of material for decontamination of waste water. The maximum removal (90%) of dyes was attained within 2 min of initiation of the adsorption process which supported the ultrafast removal efficiency. This ultrafast removal efficiency was attributed to high surface area and large concentration of -OH and CO32- groups present in NiFeTi LDH. In addition, the reusability was also performed up to three cycles with 96, 90 and 88% efficiency for methyl orange. Furthermore, the biocompatibility test on MHS cell lines were also carried which revealed the non-toxic nature of NiFeTi LDH at lower concentration (100% cell viability at 15.6 µg/ml). Overall, we offer a facile surfactant free method for the synthesis of NiFeTi LDH which is efficient for decontamination of anionic dyes from water and also non-toxic.

Mechanistic Interaction Study of Bromo-Noscapine with Bovine Serum Albumin employing Spectroscopic and Chemoinformatics Approaches.

Bromo-Noscapine (BrNs) is a tubulin-binding cytotoxic agent with significant activity against breast and lung cancer. The mechanistic interaction insight into the binding of bovine serum albumin (BSA) with BrNs can provide critical information about the pharmacodynamics and pharmacokinetics properties. Here, various spectroscopic techniques and computational methods were employed to understand the dynamics of BrNs and BSA interaction. The intrinsic fluorescence of BSA was quenched by BrNs through a static quenching procedure. The stoichiometry of BrNs-BSA complex was 1:1 and binding constant of the complex was in the order of 103 M-1 at 298 K. Based on thermodynamic analysis, it was deduced that binding process of the BrNs with BSA was spontaneous and exothermic, and the major forces between BrNs and BSA were van der waals forces and hydrogen bonding. Moreover, results of FT-IR, CD, UV spectra concluded significant conformational change in BSA on binding with BrNs. The in vitro findings were further confirmed by in silico assays. Molecular docking showed strong interactions with score of -8.08 kcal/mol. Molecular dynamics simulation analysis also suggested the stable binding with lower deviation in RMSD and RMSF values through persistent long simulation run. This study suggests optimal efficiency of diffusion of the BrNs into the bloodstream for the treatment of cancer.