A novel statistical approach for the synthesis of Chalcones viaClaisen-Schmidt condensation catalyzed by Pd nanoparticles modified mesoporous TiO2 as an efficient heterogeneous catalyst

https://doi.org/10.1016/j.colcom.2021.100461Get rights and content

Highlights

  • The study of the properties of the Pd-doped mesoporous Titania prepared materials.

  • New synthesis of chalcones catalyzed by prepared Pd nanoparticles supported on mesoporous Titania.

  • Modeling approach by Box Behnken for the optimization of chalcone yield

  • The concentration of Pd is the most important parameter in chalcone yied .

Abstract

This research emphasizes a new modeling approach by Box Behnken Design in Response Surface Methodology (RSM) for the optimization of chalcones yield based to the elaborated nanomaterials. Palladium nanoparticles (PdNPs) supported on prepared mesoporous TiO2 (Titania) are used as an ecological alternative and a new heterogeneous catalyst for the preparation and optimization of chalcones via Claisen-Schmidt Condensation (CSC). The yield of the chalcone reactions was mathematically described as a function of three parameters: PdNPs concentration, temperature and time reaction. Based on a statistical modeling and optimization process, the optimal conditions were mainly reached at the following levels: a PdNPs concentration of 0.1 wt% with a reaction temperature of 65 °C and 40 min of time. This configuration allowed reaching 99% of chalcone yield. Indeed, the results of chalcone reactions of different aromatic aldehydes in the same optimal conditions show that 0.1 wt%Pd/TiO2 catalyst is found to be highly active. Overall, the value of the adjusted coefficient of determination (R2) equal to 0.9961 indicated that the considered model was quite suitable and that the selected methodology was very efficient throughout the optimizing process. The catalyst recycle analysis shows that the PdNPs supported on Titania can be reused four consecutive times without a decrease in catalytic activity. As a general statement, this study has developed a convenient procedure for the preparation of chalcone compound in a short period of time. Moreover, the proposed approach can be served as a model in the context of green chemistry.

Introduction

In chemistry, and like any other discipline in applied sciences, it is quite common to face significant hurdle when it is about manipulating carefully materials and their parameters. This is still considered as the main challenge in many researches works in such manner more undertakings efforts must be made in the researchers' community to deeply innovate and develop modern industrial processes. In fact, the development of existing catalytic technologies for synthesis of important organic compounds is viewed as a heavy-duty challenge in research. Such advances have been at the cutting edge of research for several generations. The base-catalyzed organic transformations such Knoevenagel, aldol, Claisen–Schmidt Condensations, and transesterification reactions are of great importance in both industry and research activities.

The heterogeneous catalytic condensation of Aldol and Cross Aldol Condensation (Claisen-Schmidt) is a powerful tool for the formation of a carbon‑carbon bond in many types of carbonyl compounds [1,2]. Chalcones with α, β unsaturated carbonyl moiety is one of the most important compounds and versatile synthons for various chemical transformations. It is used as a precursor of various heterocyclic compounds [3,4].

Chalcones and their derivatives have been widely used in a large number of biological active compounds or synthetic origin exhibiting diverse pharmacological activities [5,6], such as antioxidant [2,7], anti-inflammatory [8,9], anti-cardiac [10], antifungal [11], antimalarial [12], antibacterial [13,14], anti-osteogenic [15], anti-cancer [16], anti-HIV [17], antimicrobial [18], anti-tubercular [19], antidiabetic [20], anti-leishmanial [21] and antihypertensive activities [22].

The most common used example of CSC is the synthesis of chalcones because of their importance [[23], [24], [25]]. However, heterogeneous catalysts are preferred for the synthesis of chalcones [1]. The most used ones in CSC are alkaline-doped activated carbons (Na- and Cs-Norit) [26], alumina [27], Ba(OH)2 [28], hydrotalcites [29], natural phosphates modified with sodium nitrate [1], Nanoporous AlSBA−15 [30], Hierarchical Cs-Pollucite Nanozeolite [31] andKF–Al2O3 [32].

Because of its thermal stability, PdNPs modified Titania is considered as very promising in regards to the huge number of applications in various industrial processes [[33], [34], [35], [36]]. Further, more other advantages can be cited, namely active surface area [37], porosity [38,39], specific active sites [40,41]. All these characteristics reflect the fact that PdNPs is very appropriate to use as an heterogeneous catalyst in organic synthesis.

RSM is quite possibly the most mainstream experimental design methodology considered by analysts in a wide scope of fields, particularly in chemistry where experiences need the highest level of precision [[42], [43], [44]]. The main motivation behind is the creation of an experiment environment which facilitates the building of the optimal design under the available working conditions. Further, it is generally recognized that RSM is a powerful modeling approach for understanding and analyzing different processes in chemistry field [[45], [46], [47]].It was approved in several works that the Box-Behnken design is recommended in such experimentations requiring both human attention and huge number of iterations. Hence, the major challenge is, of course, saving money and time in downstream industrial cycles. This strategy can consider and important number of variables, alongside three levels of test conditions (low, medium and high levels) [48]. For this reason, among others, the Box-Behnken design remains more efficient than the other response design techniques. Also, it should be mentioned that the Box-Behnken design effectiveness is confirmed by enabling huge number of trials and parameters to be incorporated in the process.

In one concerns of continuation in achieving a set of ongoing projects mainly focused on nanomaterials and their various applications, this research complements noteworthy efforts that are underway within our research team [38,45,[48], [49], [50], [51], [52], [53]]. It proposes an efficient, clean, economical, and easy heterogeneous reaction process for the synthesis of chalcones based on the use of PdNPs modified Titania as a new heterogeneous catalyst. Within this framework, a modeling approach by Box Behkhen Design on RSM for assessing the different parameters effects on the chalcone yield will be carried out. It permits to detect the interactions between the chosen parameters while considering the best conditions among the process.

Section snippets

Reagents

Titanium isopropoxide (IV) [C12H28O4Ti, (97%)], acetic acid [CH3 COOH, (20%)], Pluronic P123 [EO20PO70EO20, 99.99%], palladium nitrate hexahydrate [Pd (NO3)2.2H2O, (99,99%)], Ethanol [C2H5OH, (99%)],]. Acetophenone [CH3COC6H5, (≤99%), benzaldehyde [C6H5 CHO, (≤99%)], ethanol [CH3CH2OH, pure]. Every chemical product was purchased from Sigma Aldrich.

Preparation of catalyst

Mesoporous Titania was prepared by an easy hydrothermal-assistant sol-gel method using P123 as a structure-directing agent just like reported in our

Box-Behnken Design

The Box-Behnken Design was used to highlight elements supposed to be critical on the creation of chalcone reaction. Altogether, three factors were assessed and recorded in Table 1: Concentration of PdNPs on TiO2 (A), temperature of reaction (B), and a reaction time (C). Every factor was tested at three thresholds: low (− 1), central (0) and high (+1).

To distinguish the factors that effectively affect the reactions (response yield) statistical indicators were used [54,55]. All computations and

N2 adsorption–desorption isotherms

The Brunauer-Emmett-Teller (BET) theory is known as a useful method for studying the surface texture properties of materials. The N2 adsorption-desorption isotherms and pore size distribution of the prepared materials are shown in Fig. 1a. Pure Titania and Pd-doped mesoporous Titania materials exhibit type IV adsorption-isotherms characteristic of mesoporous materials according to the IUPAC [49,56]. A sharp inflection at a relative pressure around ~0.5–0.8 and a narrow pore size distribution

Conclusion

In this work, chalcones were successfully synthesized via Claisen-Schmidt condensation of aromatic aldehydes. This very simple and effective process is based on the use of PdNPs doped mesoporous Titania as a heterogeneous catalyst. The obtained yield was very promising by using 0.1Pd/TiO2 over a short period of time. The process was carried out by assessing the impact of three parameters: PdNPs concentration, temperature and time of the reaction on the yield of chalcones. The appropriateness of

Declaration of Competing Interest

The authors declare that they have no conflict of interest.

Acknowledgements

The authors are grateful to the Algerian Direction Gnérale de la Recherche Scientifique et du Développement Technologique (DGRSDT-MESRS), the University of Tlemcen and Ain Temouchent for funding this work.

References (64)

  • D. Ramesh et al.

    Indole chalcones: design, synthesis, in vitro and in silico evaluation against mycobacterium tuberculosis

    Eur. J. Med. Chem.

    (2020)
  • A. Rammohan et al.

    Design, synthesis, docking and biological evaluation of chalcones as promising antidiabetic agents

    Bioorg. Chem.

    (2020)
  • L. Alonso et al.

    Antileishmanial activity of the chalcone derivative LQFM064 associated with reduced fluidity in the parasite membrane as assessed by EPR spectroscopy

    Eur. J. Pharm. Sci.

    (2020)
  • S. Farooq et al.

    One-pot and two-pot method for Chalcone derived Pyrimidines synthesis and applications

    J. Heterocyclic Chem.

    (2021)
  • L.F. Castaño et al.

    New chalcone-sulfonamide hybrids exhibiting anticancer and antituberculosis activity

    Eur. J. Med. Chem.

    (2019)
  • E. Polo et al.

    Ultrasound-assisted synthesis of novel chalcone, heterochalcone and bis-chalcone derivatives and the evaluation of their antioxidant properties and as acetylcholinesterase inhibitors

    Bioorg. Chem.

    (2019)
  • R. Maya et al.

    An efficient and environmentally benign Bentonite–gold Nanohybrid-catalyzed oxidative cross-coupling of ketones with Benzylic primary alcohols

    Asian Journal of Organic Chemistry

    (2017)
  • M.S. Alhumaimess et al.

    Synthesis of ionic liquid intercalated layered double hydroxides of magnesium and aluminum: a greener catalyst of Knoevenagel condensation

    Journal of Saudi Chemical Society

    (2020)
  • S.J. Lee et al.

    Efficient recovery of palladium nanoparticles from industrial wastewater and their catalytic activity toward reduction of 4-nitrophenol

    Chemosphere

    (2021)
  • Y.-C. Wang et al.

    Using palladium nanoparticle-decorated lysozyme amyloid fibrils to catalyze the reduction of methylene blue

    J. Taiwan Inst. Chem. Eng.

    (2021)
  • L.L. Sikeyi et al.

    Microwave assisted synthesis of nitrogen doped and oxygen functionalized carbon nano onions supported palladium nanoparticles as hybrid anodic electrocatalysts for direct alkaline ethanol fuel cells

    Int. J. Hydrog. Energy

    (2021)
  • K. Kakaei et al.

    Synthesis of nitrogen-doped reduced graphene oxide and its decoration with high efficiency palladium nanoparticles for direct ethanol fuel cell

    Renew. Energy

    (2021)
  • S. Khaoulani et al.

    Wastewater treatment by cyclodextrin polymers and noble metal/mesoporous TiO2 photocatalysts

    Comptes Rendus Chimie

    (2015)
  • H. Ding et al.

    Label-free electrochemical immunosensor with palladium nanoparticles functionalized MoS2/NiCo heterostructures for sensitive procalcitonin detection

    Sensors Actuators B Chem.

    (2020)
  • T. Wu et al.

    Graphene-nickel nitride hybrids supporting palladium nanoparticles for enhanced ethanol electrooxidation

    Journal of Energy Chemistry

    (2021)
  • M.C. Vebber et al.

    Self-assembled thin films of PAA/PAH/TiO2 for the photooxidation of ibuprofen. Part I: optimization of photoactivity using design of experiments and surface response methodology

    Chem. Eng. J.

    (2019)
  • A. Hafeez et al.

    Optimization on cleaner intensification of ozone production using artificial neural network and response surface methodology: parametric and comparative study

    J. Clean. Prod.

    (2020)
  • X. Wang et al.

    Fluoride removal from secondary effluent of the graphite industry using electrodialysis: optimization with response surface methodology

    Frontiers of Environmental Science & Engineering

    (2019)
  • H. Chaker et al.

    A statistical modeling-optimization approach for efficiency photocatalytic degradation of textile azo dye using Cerium-doped mesoporous ZnO: A Central Composite Design in Response Surface Methodology

    Chemical Engineering Research and Design

    (2021)
  • E. Cheraghipour et al.

    Process optimization and modeling of Pb (II) ions adsorption on chitosan-conjugated magnetite nano-biocomposite using response surface methodology

    Chemosphere

    (2020)
  • H. Chaker et al.

    Photocatalytic degradation of methyl orange and real wastewater by silver doped mesoporous TiO2 catalysts

    J. Photochem. Photobiol. A Chem.

    (2016)
  • P. Kraisit et al.

    Fluconazole-loaded solid lipid nanoparticles (SLNs) as a potential carrier for buccal drug delivery of oral candidiasis treatment using the box-Behnken design

    Journal of Drug Delivery Science and Technology

    (2021)
  • Cited by (26)

    • A magnetically separable clinoptilolite supported CdS-PbS photocatalyst: Characterization and photocatalytic activity toward cefotaxime

      2023, Applied Surface Science
      Citation Excerpt :

      However, the four attacks' pathways mentioned above can mineralize molecules of pollutants into some less harmful products such as carbon dioxide and other inorganic salts [21,22]. The overall photodegradation efficiency may be low in a single semiconductor system due to the fast recombination of the photoinduced e/h pairs [23–25]. This harmful process must be overcome by applying various technologies such as metal/non-metals doping [26], coupling of two or more semiconductors (or heterostructure architects) [27–29], plasmonic systems [30–32], supporting the semiconductors onto suitable supports, nanoscale semiconductors [33–35], etc [36].

    • Chemometric study in plasmonic photocatalytic efficiency of gold nanoparticles loaded mesoporous TiO<inf>2</inf> for mineralization of ibuprofen pharmaceutical pollutant: Box Behnken Design conception

      2022, Inorganic Chemistry Communications
      Citation Excerpt :

      Such methodology generally disregards the combined effect between variables. To overcome this shortcoming, the response surface methodology combines mathematics and statistics approaches for designing an experiment environment and analyzes the relative significance of various parameters even within complicated processes [35,56]. The RSM methodologies can be used to reveal the optimal conditions of various reactions while minimizing time and costs in an industrial process.

    View all citing articles on Scopus
    View full text