Adsorption of mercaptopurine drug on the BN nanotube,nanosheet and nanocluster: a density functional theory study

ABSTRACT

We have investigated the interaction of mercaptopurine (MP) drug with BN nanotube, nanosheet and nanocluster using density functional theory calculations in the gas phase, and aqueous solution. We predicted that the MP drug tends to be physically adsorbed on the surface of BN nanosheet with an adsorption energy (E_ad) about ?3.2?kcal/mol. The electronic properties of BN nanosheet are not affected by the MP drug, and this sheet is not a sensor. But the electronic properties of BN nanotube and nanocluster are significantly sensitive to this drug in both gas phase, and aqueous solution. The BN nanocluster suffers from a long recovery time (8.8?×?10⁸?s) because of a strong interaction (E_ad?=??28.6?kcal/mol), and this cluster is not a proper sensor for MP detection. But the BN nanotube benefits from a short recovery time about 49.5?s at room temperature, and may be a promising candidate for application in the MP sensors. The water solvent decreases the strength of interaction between the BN nanotube, and MP drug, but it does not affect the electronic sensitivity of the nanotube sensibly.     

DFT study on the chemical sensitivity of C3N nanotubes toward acetone

Potential application of single-walled C₃N nanotubes was investigated as chemical sensors for acetone molecules based on the density functional theory calculations. It was found that the pristine nanotube weakly adsorbs an acetone molecule with the adsorption energy of − 9.7 kcal/mol, and its electronic properties are not sensitive to this molecule. By replacing a C atom with a Si atom, the nanotube becomes a p-type semiconductor. The adsorption energy of the acetone molecule on the Si-doped nanotube becomes much more negative (E_ad=−67.4 kcal/mol). The adsorption process leads to a sizable increase in the resistance of the Si-doped tube, thereby, it can show the presence of acetone molecule, creating an electronic signal. Also, the sensitivity of these devices can be controlled by the doping level of Si atoms. By increasing the number of dopant atoms from 1 to 4, the sensitivity is gradually increased.     

Interaction of alkanethiols with single-walled carbon nanotubes: First-principles calculations

We report the results of our first-principles study based on density functional theory on the interaction of alkanethiols with both defected and defect-free single-walled carbon nanotube (SWCNT). The adsorption energies are calculated for various configurations such as alkanethiol molecule approaching to defect sites heptagon, hexagon, and pentagon in defective tube, and another case where the alkanethiol approaching to hexagon in defect-free nanotube. The calculated results showed that alkanethiols are rather strongly bound to the outer surface of both the defected and defect-free carbon nanotubes with the binding energy of about −50.58 kcal/mol, consistent with the experimental result. We also find that alkanethiols prefer to be adsorbed on the hexagon ring site of defect-free nanotube. Furthermore, the effect of alkanethiols chain length on the adsorption of alkanethiols on carbon nanotubes has been investigated, and the obtained results reveal that the longer alkanethiols bind rather more strongly to the nanotube surface.     

Terahertz radiation from armchair carbon nanotube dipole antenna

This paper investigates the electromagnetic radiation characteristics of a metallic, large aspect ratio single walled carbon nanotube antenna in the terahertz frequency region below 12.5 THz. The key features of terahertz pulse have been revealed on the carbon nanotube antenna in comparison with conventional photoconductive switching. The terahertz waveforms, radiation power and their field distributions have been evaluated and are analysed. The Fourier transformed spectra over the whole frequency range demonstrate that the carbon nanotube antenna can be used as radiation source for broadband terahertz applications.     

基于纳观域碳纳米管的太赫兹波天线研究

基于碳纳米管独特的结构特点建立了以其为基础的Pocklington积分方程,并设计了一种全新的碳纳米管太赫兹(THz)波天线.数值仿真和理论计算结果表明,碳纳米管能够产生高频THz电磁辐射,半波长为60μm、半径为2.712nm的单壁碳纳米管偶极天线在-10dB反射系数以下可以实现2.5THz与7.6THz的双频带工作,带宽分别为8.4%与2.7%,由其构成的纳米管天线阵可以获得10.3dB的高增益特性.所得结果有助于在纳观域开展高频THz波辐射源及天线的研究与设计. 关键词： 太赫兹波 碳纳米管 天线 辐射源     

The interaction of a gold atom with carbon nanohorn and carbon nanotube tips and their complexes with a CO molecule: A first principle calculation

The interactions of a gold atom with: (a) a single-wall carbon nanohorn (SWNH) conic tip; (b) with a single-wall carbon nanotube (SWNT) tip; and (c) their complexes with a CO molecule were studied using first-principle calculations based on density functional theory. The analysis of the pyramidalization angle (θ_p) as well as the π-orbital misalignment angles indicate that there should be many reactive carbon sites on the tips of SWNH and SWNT. It was found that SWNH provides reactive sites that can more selectively interact with the target atom. We identified five sites on both the SWNT tip and the nanohorn where attachment of a gold atom leads to a stable complex. This metal is found to be bi-coordinated with the tip of SWNH, while it is mono-coordinated with the SWNT tip. The largest interaction energies are –10.75 kcal/mol and –16.17 kcal/mol, respectively. The CO probe molecule binds to Au on the Au/SWNH or Au/SWNT tips with interaction energies of –22.34 and –18.29 kcal/mol, respectively. The main contributions of the interaction with both carbon nanostructures stems from σ-donation and π-backbonding. The results suggest that SWNHs could be one of the promising candidates for the development of high-specifity nanosensors.     

多壁碳纳米管太赫兹图谱研究

近年来碳纳米管是一个重要的研究领域,但研究重点主要是其电子、光学和机械等特性。尽管有关单壁碳纳米管的在远红外光谱已有诸多报道,但多壁碳纳米管这方面的研究却较少。试验采用太赫兹时域光谱系统对多壁碳纳米管进行表征,同时也用扫描电镜对其进行形貌检测和微区成分分析,以深入了解其特性。检测结果显示,在0.2～2.0 THz内,样品折射率随着频率的增加而减小,吸收系数却随着频率的增加而增加,并可以拟合斜率为1.92的直线;样品的内径为5～15 nm、外径为15～25 nm,且长度达到了微米级,样品含C量大约为94%,其他为O和Cl杂质元素。根据泰勒扩展式和麦克斯韦方程,得到了样品在该太赫兹频域内吸收的数学模型,该数学模型基本上与检测结果一致。该样品的太赫兹吸收特性主要取决于其化学组成和分子的大小,含C量不同的碳纳米管预示着具有不同的太赫兹图谱和独特的功能。     

Computational study of singlet and triplet sulfonylnitrenes insertion into the C―C or C―H bonds of ethylene

Formation of N‐sulfonylaziridines, N‐ethylidenesulfonamides, N‐vinylsulfonamides and 4,5‐dihydro‐1,2,3‐oxathiazole 2‐oxides by the reaction of singlet and triplet trifluoromethyl‐, methyl‐ and tosylnitrenes with ethylene is studied computationally at the B3LYP/6‐311++G(d,p) level of theory in both gas phase and in solution. Singlet sulfonylnitrenes react with ethylene via [1 + 2]‐cycloaddition exothermically to give N‐sulfonylaziridines. Triplet sulfonylnitrenes are formed from the singlet ones by the intersystem crossing with the energy barrier not exceeding 2.5 kcal/mol and react in a stepwise fashion by C‐addition or H‐abstraction. The C‐addition gives rise to the formation of N‐sulfonylaziridines or N‐ethylidenesulfonamides depending on the S―N―C_sp3―C_sp2 dihedral angle, with the barrier to rotation about the N―C_sp3 bond not exceeding 2.5 kcal/mol. The H‐abstraction results in N‐vinylsulfonamides. Transformation of N‐sulfonylaziridines to N‐ethylidenesulfonamides requires to overcome the barrier of 57–60 kcal/mol, N‐ethylidenesulfonamides to 4,5‐dihydro‐1,2,3‐oxathiazole 2‐oxides—74–80 kcal/mol and N‐vinylsulfonamides to N‐ethylidenesulfonamides—about 64 kcal/mol. The use of the polarizable continuum model does not lead to a change of the course of the reaction of trifluoromethanesulfonylnitrene with ethylene and only slightly affects the relative energies of the products, intermediates and transition states. Copyright © 2014 John Wiley & Sons, Ltd.     

Solvent effects and potential of mean force study of the S_N2 reaction of CH_3F+CN~- in water

We used a combined quantum mechanics and molecular mechanics(QM/MM) method to investigate the solvent effects and potential of mean force of the CH_3F+CN~- reaction in water. Comparing to gas phase, the water solution substantially affects the structures of the stationary points along the reaction path. We quantitatively obtained the solvent effects' contributions to the reaction: 1.7 kcal/mol to the activation barrier and -26.0 kcal/mol to the reaction free energy.The potential mean of force calculated with the density functional theory/MM theory has a barrier height at 19.7 kcal/mol,consistent with the experimental result at 23.0 kcal/mol; the calculated reaction free energy at -43.5 kcal/mol is also consistent with the one estimated based on the gas-phase data at -39.7 kcal/mol.     

Ring strain energy in ether‐ and lactone‐containing spiro compounds

Ring strain energies (RSEs) have been calculated for oxygen‐containing spiro compounds using the group equivalent reaction (GER) formalism. The RSEs for all compounds studied were calculated from the energies of fully‐optimized structures at the MP2 + ZPE/cc‐pVDZ level and the more computationally costly G4(MP2) method. RSEs for selected compounds were also calculated with the CBS‐QB3 method, with less than 1 kcal/mol difference observed between G4(MP2) and CBS‐QB3. The difference between the less costly MP2 + ZPE and G4(MP2) methods was less than 1.5 kcal/mol. The highest RSEs were found for the compounds containing two three‐membered rings, and these compounds also exhibited the greatest excess strain energy (ESE) of about 12 kcal/mol. The RSEs of cyclic lactones vary with ring size differently than those of cyclic ethers. Cyclic ethers' RSEs decrease by a small amount from the three‐ to four‐membered rings then decrease drastically as the ring increases to 5 atoms, and approaches zero for the six‐membered ring, the same unexpected behavior as seen in cycloalkanes. Cyclic lactones' RSEs decrease linearly to almost zero from the three‐ to the five‐membered ring, then increase by 1–2 kcal/mol in the six‐membered ring. Lactone‐containing spiro compounds exhibit regularly diminishing ESE as the size of the lactone ring increases, down to about 3 kcal/mol in the δ‐lactone‐containing spiro compound. Substitution of methyl groups decreases RSE in these oxygen‐containing spiro compounds, while substitution of fluorine significantly increases RSE, as has been reported in other compounds. But RSE alone is shown to not correlate completely with chemical reactivity of these spiro compounds. Copyright © 2014 John Wiley & Sons, Ltd.     

Amplification of terahertz radiation in carbon nanotubes

We investigate theoretically the feasibility of amplification of terahertz radiation in aligned achiral carbon nanotubes, a zigzag (12,0) and an armchair (10,10) in comparison with a superlattice using a combination of a constant direct current (dc) and a high-frequency alternate current (ac) electric fields. The electric current density expression is derived using the semiclassical Boltzmann transport equation with a constant relaxation time. The electric field is applied along the nanotube axis. Analysis of the current density versus electric field characteristics reveals a negative differential conductivity behavior at high frequency, as well as photon assisted peaks. The photon assisted peaks are about an order of magnitude higher in the carbon nanotubes compared to the superlattice. These strong phenomena in carbon nanotubes can be used to obtain domainless amplification of terahertz radiation at room temperature.     

Working Mechanism of a BC3 Nanotube Carbon Monoxide Gas Sensor

Carbon and BN nanotubes have previously demonstrated extreme sensitivity to several molecules, but they cannot be used to detect highly toxic molecules of CO. In this work, we examine the possibility of a BC₃ nanotube (BC₃NT) as a potential gas sensor for CO detection by using density functional theory calculations. It is found that CO molecule can be absorbed on B and C atoms of BC₃NT wall with adsorption energies in the range of -1.0 to -25.9 kcal/mol and it can donate finite charge to the tube. By comparing the HOMO/LUMO energy gaps of the bare and CO adsorbed nanotubes, we deduce that molecular CO can induce significant change in the electrical conductivity of the tube. The conductivity change can generate an electrical signal, which might be useful for CO detection.     

The conductivity of single walled nanotube films in Terahertz region

The conductivity of single-walled nanotube films is investigated with a combination of Maxwell–Garnett (MG) and Drude–Lorentzian (DL) model in terahertz region. A theoretical investigation for the recent experiment is given and a decrease of the real conductivity with increasing frequency is predicted. Meanwhile, the real part of dielectric function of single-walled carbon nanotube films is displayed.     

Theoretical study of the adsorption of CO2 on tungsten carbide nanotubes

The adsorption of CO₂ on the single-walled tungsten carbide nanotubes has been investigated employing density functional theory method. The center of a hexagon of tungsten and carbon atoms in sites on tungsten carbide nanotube surfaces is the most stable adsorption site for CO₂ molecule, with a binding energy of −1.68 eV (−38.72 kcal/mol) and a WO binding distance of 1.95 Å. Furthermore, the adsorption of CO₂ on the single-walled carbon nanotubes has been investigated. Our first-principles calculations predict that the CO₂ adsorptive capacity of tungsten carbide nanotubes is about quadruple that of carbon nanotubes. This might have potential for greenhouse gas detection and bioremediation.     

Mechanism of 4‐methyl‐1,2,4‐triazol‐3‐thiole reaction with formaldehyde. A DFT study

Contrary to the typical nucleophilic substitution, occurring on the sulfur atom of 4‐methyl‐1,2,4‐ triazol‐3‐thiole, the reaction with formaldehyde leads to the formation of the N? C bond rather than the S? C bond. The mechanism of this reaction has been characterized theoretically. Calculations indicate that the reaction proceeds via a cyclic transition state involving one solvent molecule with the Gibbs free activation energy of only 2 kcal/mol. The alternative pathway that leads to the S? C bond formation is about 5 kcal/mol more energetically demanding. Copyright © 2007 John Wiley & Sons, Ltd.     

Computational study of singlet and triplet sulfonylnitrenes insertion into 1,3‐butadienes: 1,2‐ or 1,4‐cycloaddition?

The formation of N‐trifluoromethylsulfonyl‐2‐vinylaziridine and N‐trifluoromethylsulfonyl‐3‐pyrroline by the reaction of the singlet and triplet trifluoromethanesulfonylnitrenes with s‐cis‐ and s‐trans‐1,3‐butadienes was studied theoretically at the B3LYP/6‐311++G(d,p) and M06‐2X/6‐311++G(d,p) levels of theory. The singlet trifluoromethanesulfonylnitrene adds to s‐cis‐ and s‐trans‐1,3‐butadiene exothermally in one step to give the product of 1,2‐cycloaddition, N‐trifluoromethylsulfonyl‐2‐vinylaziridine, the energy decreasing by 88.5 and 86.2 kcal/mol at the B3LYP level and by 105.2 and 103.0 kcal/mol at the M06‐2X level, respectively. The formed 2‐vinylaziridine can undergo rotation about the C(2)–C_sp2 bond with the barrier not exceeding 3.5 kcal/mol and to rearrange into N‐trifluoromethylsulfonyl‐3‐pyrroline. The triplet trifluoromethanesulfonylnitrene reacts with s‐cis‐ and s‐trans‐1,3‐butadiene in two steps. The first exothermic step is the formation of the triplet diradical adducts. The second step is the spin inversion with the energy raising by 5.8 and 17.8 kcal/mol at the B3LYP level and by 11.0 and 20.8 kcal/mol at the M06‐2X level for the adducts to s‐cis‐ and s‐trans‐1,3‐butadiene, respectively. Recombination of the radical centers occurs selectively to give N‐trifluoromethylsulfonyl‐2‐vinylaziridine that is exothermally rearranged into N‐trifluoromethylsulfonyl‐3‐pyrroline with the energy barrier of 40 kcal/mol at the B3LYP level and of 50 kcal/mol at the M06‐2X level. Copyright © 2014 John Wiley & Sons, Ltd.     

SIMULATION OF CARBON NANOTUBE THz ANTENNA ARRAYS

A novel THz antenna structure, made of carbon nanotube arrays is suggested. Using CST MICROWAVE STUDIO (CST MWS), the capabilities of carbon nanotube terahertz (THz) antenna arrays have been simulated. The dependence of gain, upon geometrical factors, e.g., nanotube diameter, nanotube length and the inter-tubes distance, is shown. The directivity patterns of antenna arrays and the surface current distribution of an antenna have been shown by simulation. These results could be used in the design of carbon nanotube THz antenna arrays.     

Can tetra‐tert‐butylethylene be formed by ion–ion recombination or ion–molecule reaction of two di‐tert‐butylcarbene units?—a DFT study

The reaction channels of di‐tert‐butylcarbene ( 2 ), its radical anion, ( 3 ) and its radical cation ( 4 ) were investigated theoretically by using DFT/B3LYP with 6‐31+G(d) basis set and 6‐311+G(2d,p) for single point energy calculations. Conversion of the neutral carbene 2 to the charged species 3 and 4 results in significant geometric changes. In cation 4 two different types of C? (CH₃)₃ bonds are observed: one elongated sigma bond called “axial” with 1.61 Å and two normal sigma bonds with a bond length of 1.55 Å. Species 2 and 4 have an electron deficient carbon center; therefore, migration of CH₃ and H is observed from adjacent tert‐butyl groups with low activation energies in the range of 6–9 kcal/mol like similar Wagner–Meerwein rearrangements in the neopentyl‐cation system. Neutral carbene 2 shows C? H insertion to give a cyclopropane derivative with an activation energy of 6.1 kcal/mol in agreement with former calculations. Contrary to species 2 and 4 , the radical anion 3 has an electron rich carbon center which results in much higher calculated activation energies of 26.3 and 42.1 kcal/mol for H and CH₃ migrations, respectively. NBO charge distribution indicates that the hydrogen migrates as a proton. The central issue of this work is the question: how can tetra‐tert‐butylethylene ( 1 ) be prepared from reaction of either species 2 , 3 , or 4 as precursors? The ion–ion reaction between 3 and 4 to give alkene 1 with a calculated reaction enthalpy of 203.5 kcal/mol is extremely exothermic. This high energy decomposes alkene 1 after its formation into two molecules of carbene 2 spontaneously. Ion–molecule reaction of radical anion 3 with the neutral carbene 2 is a much better choice: via a proper oriented charge–transfer complex the radical anion of tetra‐tert‐butylethylene (11) is formed. The electron affinity of 1 was calculated to be negligible. Copyright © 2010 John Wiley & Sons, Ltd.     

Working Mechanism of a BC_3 Nanotube Carbon Monoxide Gas Sensor

Carbon and BN nanotubes have previously demonstrated extreme sensitivity to several molecules, but they cannot be used to detect highly toxic molecules of CO. In this work, we examine the possibility of a BC3 nanotube (BC3NT) as a potential gas sensor for CO detection by using density functional theory calculations. It is found that CO molecule can be absorbed on B and C atoms of BC3 NT wall with adsorption energies in the range of 1.0 to 25.9 kcal/mol and it can donate finite charge to the tube. By comparing the HOMO/LUMO energy gaps of the bare and CO adsorbed nanotubes, we deduce that molecular CO can induce significant change in the electrical conductivity of the tube. The conductivity change can generate an electrical signal, which might be useful for CO detection.     

A theoretical study of CHx chemisorption on the Ni(100) and Ni(111) surfaces

Cluster model calculations have been performed for CH_x, x = 0−3, chemisorbed on Ni(100) and Ni(111). The predicted chemisorption energies, at the present level of theory, based on bond-prepared clusters for Ni(100) are for carbon 150 kcal/mol, for CH 136 kcal/mol, for CH₂ 91 kcal/mol and for CH₃ 46 kcal/mol. The corresponding energies for Ni(111) are for CH 120 kcal/mol, for CH₂ 88 cal/mol and for CH₃ 49 kcal/mol. These chemisorption energies lead to similar stabilities for all CH_x fragments on both Ni(100) and Ni(111). Large basis sets and multi-reference correlation treatments are found to be very important in particular for the multiply bonded species. The vibrational C-H stretching frequencies predicted for CH_x on Ni(111) are for CH 3054 cm⁻¹ (2980 cm⁻¹), for CH₂ 3204 cm⁻¹ and for CH₃ 2709 cm⁻¹ (2680 cm⁻¹), where the available experimental values are given in parent The predicted ionization spectra of adsorbed CH_x are also in general agreement with experimental findings.