Adsorption of Si₆O₁₂ on CNTs in view point of NMR shielding tensors and NBO analysis: A novel material for drug delivery

Introduction

SWCNTs have considered as the leading candidate for nano-device applications because of their one-dimensional electronic bond structure, molecular size, and biocompatibility, controllable property of conducting electrical current and reversible response to biological reagents hence SWCNTs make possible bonding to polymers and biological systems such as DNA and carbohydrates [28-35].

The carbon nanotube (CNT) is a representative nano-material. CNT is a cylindrically shaped carbon material with a nano-metric-level diameter [1-15].

Its structure, which is in the form of a hexagonal mesh, resembles a graphite sheet and it carries a carbon atom located on the vertex of each mesh. The sheet has rolled and its two edges have connected seamlessly [12-30].

Although it is a commonplace material using in pencil leads, its unique structure causes it to present characteristics that had not found with any other materials. CNT can be classified into single-wall CNT, double-wall CNT and multi-wall CNT according to the number of layers of the rolled graphite [22-42].

The type attracting most attention is the single-wall CNT, which has a diameter deserving the name of “nanotube” of 0.4 to 2 nanometers. The length is usually in the order of microns, but single-wall CNT with a length in the order of centimeters has recently released [42-50].

CNT can be classified into single-wall CNT, double-wall CNT and multi-wall CNT according to the number of layers of the rolled graphite. The type attracting most attention is the single-wall CNT, which has a diameter deserving the name of “nanotube” of 0.4 to 2 nanometers [50-63].

Its structure, which is in the form of a hexagonal mesh, resembles a graphite sheet and it carries a carbon atom located on the vertex of each mesh. The sheet has rolled and its two edges have connected seamlessly [60-74].

The length is usually in the order of microns, but single-wall CNT with a length about centimeters have recently released. The extremities of the CNT have usually closed with lids of the graphite sheet [71-81].

The lids consist of hexagonal crystalline structures (six-membered ring structures) and a total of six pentagonal structures (five-membered ring structures) placed here and there in the hexagonal structure [79-95]. The first report by Iijima was on the multiwall form, coaxial carbon cylinders with a few tens of nanometers in outer diameter. Two years later single walled nanotubes were reported.

The carbon nanotube (CNT) is a representative nano-material. CNT is a cylindrically shaped carbon material with a nano-metric-level diameter [94-98].

Figure 1: Si6O12 & Si7O14 binding to (10,10)CNTs in different direction  a)via Oxygen b) Via Silicone   Click here to View figure

 

In the NBO analysis, the interaction arising from electron delocalization are analyzed by selecting a number of natural bonding and anti-bonding orbitals that distort from the idealized Lewis structure, caused by interactions among them through hyper-conjugative or electrostatic interactions. In NBO analysis, the input atomic orbital basis set is transformed via natural atomic orbitals (NAOs) and natural hybrid orbital (NHOs) into NBO.  In the present theoretical study, particular attention has been paid to the structural properties of The Si6O12-CNTs and Si7O14-CNTs   systems. So, the NBO analysis gives supplementary information of the relative structural properties. It should be noted that conjugated systems, such as benzene and p-conjugated linear molecules, have been well studied with NBO analysis.

Computational Details

Calculations were performed using an all-electron linear combination of atomic orbitals Hatree–Fock (HF) and density functional theory (DFT) calculations using the Gaussian 03 package. The optimizations of antibiotics and Si₆O₁₂ are carried out including exchange and correlation contributions using Beckẻs three parameter hybrid and Lee-Yang-Parr (LYP) correlation [B3LYP]; including both local and non local terms. We have geometric optimization calculation at the HF/6-31G, HF/6-31G**, HF/6-311G**. We have also performed a geometric optimization calculation at the B3LYP/6-31G, B3LYP/6-31G** and B3LYP/6-31G** level.

The NMR isotropic shielding constants were calculated using the standard GIAO (Gauge-Independent Atomic Orbital) approach of Gaussian 03 program package.

a) The isotropic value σ_iso of the shielding tensor which can be defined as:

 

Results and Discussion

We studied about Si₆O₁₂ and Si₇O₁₄ molecules as the novel material for drug delivery.

Before and after connecting to the CNTs. NMR and NBO calculations were performed in electric field of charges. NMR and NBO parameters are listed in tables 1-5 in different levels and different basis sets.
HOMO and LUMO and Gap energy of MWC-Nano-cones are listed in Table1.

Contour line map of Localized orbital Locator (LOL) and Relief map (Shaded Surface map with projection) for electron density of Si₆O₁₂ are shown in Fig2 & 3. electron Localization Function of Si₆O₁₂ is shown in Fig 4.

(Figure 2: Contour line map of Localized orbital Locator (LOL   Click here to View figure

 

Figure 3: Shaded Surface map with projection of electron density including 5 sharp peak and one blunt  Click here to View figure

 

Figure 4: electron Localization Function of Si6O12   Click here to View figure

 

The situation of Si₆O₁₂ adsorption over CNTs and The situation of Si₇O₁₄ are shown in Fig1. Considering the optimized structure, the NMR shielding tensors were calculated then these parameters were used to show active sites in this structure. The results of б_iso, б_aniso, δ, Δб and η for this nano-cone in the same methods and basis sets are shown in table 2. Finally the charts of б_iso, б_aniso, δ and η for the atoms of Si₆O₁₂ Si7O14in 6-31G,  6-311G**,  level of theory and B3LYP method. We can obtain the interesting results from the NMR charts. Comparison of these charts (бiso, бaniso, δ and η) shows that some of peaks in these charts are similar to each other. If these peaks are reviewed, we can understand which similar atoms are situated in the same peaks of different charts. The comparison of these peaks shows that three atoms are exactly repeated in бiso, бaniso, δ and η charts. These three atoms are the active sites in these structures.  In general, the chart of electronic charge in different methods and basis sets is similar to the charts of NMR parameters Silicon atoms have more electrons than oxygen atoms.

So we can find that most chemical shielding. The concavity points are created due to the change of negative charge into a positive charge.

The electron density figure show that the mechanism of positive charge is different from negative charge. Positive and negative areas are completely different.

The results show that the heterocycle drugs connect to Si₆O₁₂ is stronger than Si₇O₁₄.

NBO analysis of the Si6O12 and Si7O14 system at the level of B3LYP/6-31g theory with different has been given in Table 3-6. The coefficients of s and p orbitals of both Si-O in Si6O12 and Si7O14 bonds can be distinguished based on these NBO data. Based on the constant values of the coefficients of linear combination of s and p orbitals of different bonds, a specific voltage differences could be expected. Summary of Natural Population analysis and Natural Population is listed in Table 3.Natural electron configuration of Valance and core electrons is listed in table 4. Occupancy, geminal, vicinal, energy, NBO, Principal delocalization is listed in Table 6.

Table 1  Click here to View table

 

Table 2: NMR parameters of Silicon andOxygen in Si₆O₁₂CNTs and Si₇O₁₄CNTs at the different levels

Table 3: Summary of Natural Population Analysis Natural Population  Click here to View table

 

Table 4: Natural Electron Configuration A to m No valance/core  Click here to View table

 

Table 5: Natural Bond Orbital Analysis Occupancies Lewis Structure Low High  Click here to View table

 

Table 6: Natural Bond Orbitals Summary) Principal Delocalization NBO Occupancy Energy geminal, vicinal, remote. Click here to View table

 

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