Characterization of a Zeolite-Y-Encapsulated Zn(II)Salmphen Complex with Targeted Anticancer Property.

Resistance and severe side effects of classical chemotherapeutic drugs are major challenges to cancer therapy. New therapeutic agents and combination therapy are considered potential solutions that enhance the efficacy of the drug as well as reduce drug resistance. The success of a platinum-based anticancer drug, cisplatin, has paved the way to explore metal-centered anticancer therapeutic agents. Herein, the zeolite-Y-encapsulated Zn(II)Salmphen complex is synthesized using a flexible ligand approach. The Zn(II)Salmphen complex and its encapsulation within the supercage of zeolite-Y were characterized by elemental analysis, Fourier transform infrared (FTIR) spectroscopy, UV-vis, fluorescence, powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), NMR, and high-resolution mass spectrometry (HRMS) techniques. Elemental analysis, PXRD, and SEM, all together confirm the integrity of the zeolite framework after the encapsulation of Zn(II)Salmphen complex in it, and elemental analysis provides the Si/Al ratio and Zn content present. FTIR and XPS studies indicate the successful encapsulation of the complex. NMR and HRMS studies confirm that the Zn(II)Salmphen complex is dimer; however, within the supercage of zeolite-Y, it is expected to exist as a monomer. The extent of structural modification of the encapsulated Zn(II)Salmphen complex is intimated by electronic spectroscopic studies. The free-state Zn(II)Salmphen is a fluorescent complex, and even the encapsulated Zn(II)Salmphen complex, when taken in dimethyl sulfoxide (DMSO), shows fluorescence. In comparison to cisplatin, encapsulated Zn(II)Salmphen complex displays comparable cytotoxicity (IC50 = 2.0 ± 0.5 µg/mL at 48 h) toward breast cancer cell line, whereas free Zn(II)Salmphen has better cytotoxicity (IC50 = 1.5 ± 0.5 µg/mL at 48 h). Importantly, elemental analysis has revealed that the IC50 value, if calculated only in terms of Zn(II)Salmphen within Zn(II)Salmphen-Y, is as low as 54.59 ng/mL, indicating a very high efficacy of the drug. Interestingly, a 48 h treatment with the encapsulated Zn(II)Salmphen complex shows no toxicity toward immortal noncancerous keratinocyte cells (HaCaT), whereas cisplatin has an IC50 value of 1.75 ± 0.5 µg/mL. Internalization studies indicate that zeolite-Y targets cancer cells better than it does noncancerous ones. Hence, cellular uptake of the zeolite-encapsulated Zn(II)Salmphen complex in cancer cells is more than that in HaCaT cells, resulting in the generation of more reactive oxygen species and cell death. Significant upregulation of DNA damage response protein indicates that DNA-damage-induced cellular apoptosis could be the mechanism of drug action. Overall, the zeolite-encapsulated Zn(II)Salmphen complex could be a better alternative to the traditional drug cisplatin with minimal effect on noncancerous HaCaT cells and can also be utilized as a fluorescent probe in exploring the mechanistic pathway of its activity against cancer cells.

Importance of the Nature of Acidic Sites of Different Aluminosilicates on Fixation of Carbon Dioxide with Styrene Oxide.

The nature of acidic sites in commercially available aluminosilicates, zeolite Na-Y, zeolite NH4 + -ZSM-5, and as-synthesized Al-MCM-41 have been investigated by employing them as catalysts for capturing CO2 by styrene oxide. The catalysts, in tandem with tetrabutylammonium bromide (TBAB), produce styrene carbonate, and the yield of the product is observed to be governed by the acidity of the catalysts and hence, the Si/Al ratio. All these aluminosilicate frameworks have been characterized by IR, BET, TGA, and XRD. XPS, NH3 -TPD, and 29 Si solid-state NMR studies have been carried out to analyze the Si/Al ratio and the acidity of these catalysts. According to TPD studies, the number of weak acidic sites of these materials follow an order as NH4 + -ZSM-5 < Al-MCM-41 < zeolite Na-Y, which is just in accordance with their Si/Al ratios and the yield of the cyclic carbonates obtained, i. e., 55.3 %, 68 %, and 75.4 % respectively. The TPD data and the yield of the product carried out with calcined zeolite Na-Y indicate that not only the weak acidic sites but also the role of strong acidic sites might appear crucial in the cycloaddition reaction.

An insight into the catalytic activity of palladium Schiff-base complexes towards the Heck coupling reaction: routes via encapsulation in zeolite-Y.

A small set of palladium Schiff-base complexes were synthesized and entrapped in the supercage of zeolite-Y. All these novel complexes in both states were systematically characterized with the help of different characterization tools like XRD, SEM-EDS, thermal analysis, XPS, IR, electronic spectroscopic and theoretical studies. These systems were thoroughly studied for their catalytic activities towards the Heck coupling reaction between bromobenzene and styrene. The aim was to meticulously compare the performance of the homogeneous catalysts, i.e., neat palladium Schiff-base complexes with that of their heterogeneous encapsulated analogs. The experimental as well as theoretical electronic structure studies suggested significant structural modification of the guest Pd(ii)-Schiff-base complexes after encapsulation in zeolite Y. These complexes manifested modified catalytic activities towards the Heck coupling reaction. The theoretical studies reinforced the correlation between the modified catalytic properties and structural alteration of these complexes on encapsulation. These heterogeneous catalysts essentially demonstrated the benefits of easy separation and reusability as compared to the homogeneous analogues.

Palladium-Schiff Base Complexes Encapsulated in Zeolite-Y Host: Functionality Controlled by the Structure of a Guest Complex.

A series of palladium complexes of tetradendate Schiff base ligands L1 ( N,N'-bis(salicylidene)phenylene-1,3-diamine) and its derivatives L2 and L3 have been synthesized by using the "flexible ligand method" within the supercage of zeolite-Y. These complexes in both their free and encapsulated states have been thoroughly characterized with the help of different characterization tools such as XRD, SEM-EDS, BET, thermal analysis, XPS, IR, and UV-vis spectroscopic studies. All these encapsulated complexes are identified with a dramatic red shift of the d-d transition in their electronic spectra when compared with their free states. Theoretical as well as experimental studies together suggest a substantial modification of the structural parameters of square planar Pd(II)-Schiff base complexes upon encapsulation within the supercage of zeolite-Y. Encapsulated complexes are also subject to show modified catalytic activities toward the Heck reaction. These heterogeneous catalysts can easily be separated from the reaction mixture and reused.

Tuning of Catalytic Property Controlled by the Molecular Dimension of Palladium-Schiff Base Complexes Encapsulated in Zeolite Y.

Planar palladium-Schiff base complexes are synthesized, maintaining the order of their molecular dimensions as PdL1 < PdL2 < PdL3 < PdL4 < PdL5 in free state, as well as encapsulated in zeolite Y, where L1: N,N'-bis(salicylidene)ethylenediamine and L2, L3, L4, and L5 are derivatives of L1. All encapsulated complexes have shown better catalytic activity for the sulfoxidation of methyl phenyl sulfide in comparison to their homogeneous counter parts. These hybrid systems are characterized with the help of different characterization techniques such as X-ray diffraction analysis, scanning electron microscopy-energy-dispersive X-ray spectrometry, X-ray photoelectron spectroscopy, Fourier transform infrared, and UV-visible spectroscopy; all of these studies have suggested that the largest complex deviates by the maximum from its free-state properties, and a radical change in the reactivity of the complex is observed.

Enhanced catalytic activity and magnetization of encapsulated nickel Schiff-base complexes in zeolite-Y: a correlation with the adopted non-planar geometry.

Square planar Ni(ii)-Schiff base complexes when encapsulated in a supercage of zeolite Y have shown altered optical, magnetic properties and catalytic activities in comparison to their corresponding free states. Different characterization techniques like XRD analysis, SEM-EDX, AAS, FTIR, UV-Visible spectroscopy and magnetic studies as well as detailed theoretical studies altogether show the differences in the properties of complexes in free and encapsulated states. All these studies have suggested that the largest complex deviates by the maximum amount from its free-state properties and a fascinating correlation between the extent of deviation from molecular dimension and modified catalytic activity of encapsulated complexes is observed.

Encapsulation of a Ni salen complex in zeolite Y: an experimental and DFT study.

It is observed that for a square planar Ni(II)-Schiff base complex of the general formula {Ni(II)L}, where L is {L: N,N'-bis(5-hydroxy-salicylidene)ethylenediamine}, when encapsulated in a supercage of zeolite Y the bulky guest complex adopts a non-planar geometry without disturbing the integrity of the zeolite framework. Detailed comparative characterization is carried out to understand the structural change of the guest complex as a result of steric and electronic interactions with the host framework. UV-Vis spectroscopic studies of the encapsulated and 'neat' complex show a significant blue shift in the d-d transition after encapsulation and the diamagnetic 'neat' complex exhibits paramagnetism after encapsulation. DFT studies of the Ni(II)-Schiff base complex have been carried out for different spin states in neat and encapsulated form and the UV-Vis spectra are simulated using TD-DFT to understand the observed spectra in detail.

Encapsulation of cobalt phthalocyanine in zeolite-y: evidence for nonplanar geometry.

Cobalt (II) phthalocyanine (CoPc) molecules have been encapsulated within the supercage of zeolite-Y. The square-planar complex, being larger than the almost spherical cage, is forced to adopt a distorted geometry on encapsulation. A comparative spectroscopic and magnetic investigation of CoPc encapsulated in zeolite-Y and in the unencapsulated state is reported. These results supported by molecular modeling have been used to understand the nature and extent of the loss of planarity of CoPc on encapsulation. The encapsulated molecule is shown to be the trans-diprotonated species in which the center of inversion is lost due to distortions required to accommodate the square complex within the zeolite. Encapsulation also leads to an enhancement of the magnetic moment of the CoPc. This is shown to be a consequence of the nonplanar geometry of the encapsulated molecule resulting in an excited high-spin state being thermally accessible.