Mediated self-assembly of host-guest nano copper cyanide and 1,7-diaminoheptane: Design, catalytic and biological evaluation
Introduction
During the research of functional materials, supramolecular coordination polymers (SCPs) have remarkable performance not just because of their structural diversity but also for their extensively high thermal stability [1]. SCPs can be considered as the polymeric form of supramolecular complexes. In this case, the metal ions are together connected through the organic ligands [2]. The role of SCPs, as one of the most extreme significant inorganic-organic hybrid materials, has as of late been stretched out into the area of material science over different fields including, as example but not restricted, magnetism, catalysis, luminescence, sensing, gas storage, and detection [3], [4], [5], [6]. For the time being, the functionalization of SCPs is the primary center, which offers driving force to the improvement of SCPs incredibly, making them conceivable to use in batteries, supercapacitors, in addition to fuel cells [7]. SCPs is a subfield of supramolecular chemistry which typically include a scope of well-known non-covalent driving forces such as ionic interactions, hydrogen bonds, hydrophobic forces, and host–guest interactions [8], [9], [10], [11]. So, the synthesis and characterization of SCPs, with well-defined sizes, shapes, and chemical environments have accomplished significant advancement in materials science. A basic advance to build such materials is to choose or configurate fitting linkers which can coordinate with the metal centers to design network of high dimensionality [12]. Host-guest system can be used to fabricate SCPs in which the host encapsulates the gust via different unconventional intermolecular interactions. They exhibit wide applications in adsorption, catalysis, and magnetism. Albeit these systems are amazingly encouraging, the sensible combination of host–guest compounds is as yet an intense objective. In addition, types of coordination atoms and the geometry of the ligand highly have effect for creation of end materials [13]. The efflorescence of nanomaterials has prompted to the development of green and sono-chemical chemistry. Sono-chemical radiation is a facile, cost-effective, and environmentally friendly route [3, 14]. Self-assembly of coordination polymer nanoparticles (CPNs), which is one of the principle parts of supramolecular chemistry has quickly acquired impressive consideration due to the vast majority of these CPNs which are biologically compatible, environmentally friend, and their intrinsic luminescence features have potential applications in various fields [15,16]. Owing to the afore mentioned advantages, supramolecular strategies have proven to be a meaningful tool in the construction of artificial supramolecular nanomaterials [17]. Many factors have important role for construction of SCPs such as organic linkers, metal ions, pH, reaction temperature and solvent. The selection of suitable ligands is the most important parameter [18]. Amino complexes of transition metals exhibit significant applications in numerous fields [19]. Polyamine is used to perform the bridging function to create complex materials exhibiting potential applications [20], [21], [22], [23], [24]. Also, the functionality of a diamine can be affected by introducing different substituents [25], [26], [27], [28]. Organo-diimines are amongst ligands which had been utilized for creation of SCPs networks containing copperI cyanide [26], [27], [28], [29], [30], [31]. However, aliphatic diamines had been only studied with silverI thiocyanate, silverI cyanide and one example with silverI azide [32], [33], [34] as well as aliphatic diamines starting from ethylenediamine to 1,6-Diaminohexane with [Cun(CN)m]x− anion [33], [34], [35] as far as we known. Broadening our research work the construction and properties of bimetallic nitrogen containing organic ligands, we had tried to synthesize SCP based on long chain aliphatic diamine, 1,7-diaminoheptane (DAHP), copper (I)cyanide in the presence of Me3SnCl. However, a tin free of new nano-scaled 3D-host-guest supramolecular coordination polymer (SCP1); ∞3[(Cu3(CN)3)2.(DAHP)], has been obtained. Spectral characteristics of SCP1 were investigated. The catalytic and photocatalytic activities of SCP towards hazardous MV, MB and IC dyes as pollutants were studied. On the other hand, the antitumor activity in vitro against various human cancer cell lines and their antioxidant, antihemolytic, antibacterial and antifungal activities were also estimated (Scheme 1).
Section snippets
Materials and physical measurements
K3[Cu(CN)4] was synthesized according to the literature procedures [35]. The used solvents and chemicals were of analytical grade supplied and utilized as received. Experimental procedures, spectrophotometers and equipment are the same as those were reported elsewhere [35, 36].
Synthesis of nanosized ∞3[(Cu3(CN)3)2.(DAHP)] SCP 1
An aqueous solution of K3[Cu(CN)4] [178 mg (0.63 mmol)] had been dropwise added to a mixture of acetonitrile solutions of Me3SnCl [380 mg (1.9 mmol)] and 1,7-diaminoheptane (DAHP) [82 mg (0.63 mmol)] which had been
Characterization of the nanostructure of SCP1 using TEM and SEM measurements
TEM images of SCP1 support its nanostructure with particle. size in the. range of 2.21- 14.89 nm, Figs S1a and b. The morphology exhibits regular nanostructures and narrower morphology. The distribution of diameters of the nanoparticles was estimated by a histogram which represents a general estimation of the probability distribution of a continuous series of variable diameters of nanoparticles. The frequency of occurrences of each nanoparticle is indicated by the area of the bar. Figs S1 c and
IR and 1H-NMR spectra
Cyanide stretching vibrations; ν(CN), can be considered as a characteristic absorption peak in the IR- spectra of SCPs having cyanide group. It is well known that the cyanide frequencies close to those of genuine salt are attributed to Cu-CN-Cu linear bridging while bands higher than those of the salt exhibit terminal or nonlinear bridging CN groups [54], [55], [56]. The IR-spectrum of SCP1, Fig. S4, shows two bands at 2084 and 2108 cm−1 due to νCN which support nonlinear bridging [(Cu3(CN)3)2]
Thermogravimetric analysis
SCP1 thermogravimetric analysis was carried out under nitrogen atmosphere. SCP1 was stable up to 200°C after which it suffers thermal decomposition in four stages, Table 2.
The steps one and two are owing to loss of 1,7-DAHP within the range of 200 - 350°C. The first step is owing to loss of [NH2(CH2)3] at 200-250°C; Δ% obser.(calc.) 8.91 (9.86) while the second one represents loss of [NH2(CH2)4] at 260-350°C; Δ% obser.(calc.) 10.79 (10.78), Table 2. The third step is due to decomposition of the
Catalytic investigation
Nowadays wastewaters contain large quantities of organic dyes which are responsible of serious problems to the eco-system where they are chemically stable and biodegradable inactive [57, 58]. Besides the related and previous work, the present work contributes to the development of various dye degradation systems [59], [60], [61]. So, methyl violet (MV), methylene blue (MB) and indigo carmine (IC) dyes were chosen as examples of pollutants for mineralization process to estimate the catalytic
Antioxidant activity using ABTS inhibition, erythrocyte hemolysis and DNA binding
ABTS assay and rate erythrocyte hemolysis were used to test the antioxidant activity of SCP1. The results of ABTS assay indicated that SCP1 has excellent anti-oxidative activity compared to that of ascorbic acid, Table 3. The obtained values of SCP1 are close to the data of ascorbic acid. Also, SCP1 has good anti-hemolytic activity relative to ascorbic acid, Table 3. DNA can reversibly bind to methyl green forming colored DNA/methyl green complex which is stable at neutral pH while free methyl
Conclusions
The structure of supramolecular coordination polymer; ∞3[(Cu3(CN)3)2.(DAHP)], (SCP1), consists of new two-fold [Cu3(CN)3]2 units containing tetrahedral copper(I) atoms that are arranged in unique way to create 3D-network of remarkable wide cavities enable to capsulate the long chain DAHP as guest molecule. The nanosized SCP1 act as heterogeneous catalyst for efficient degradation of methyl violet (MV), methylene blue (MB) and indigo carmine (IC) dyes in the presence of H2O2 as oxidant within
Declaration of Competing Interest
The authors declare that there is no conflict of interest.
Acknowledgement
The authors are thankful to Tanta University, Tanta, Egypt that supports this work.
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