A series of ruthenium azopyridine complexes have recently been investigated due to their potential cytotoxic activities against renal cancer (A498), lung cancer (H226), ovarian cancer (IGROV), breast cancer (MCF-7) an...A series of ruthenium azopyridine complexes have recently been investigated due to their potential cytotoxic activities against renal cancer (A498), lung cancer (H226), ovarian cancer (IGROV), breast cancer (MCF-7) and colon cancer (WIDR). Thus, in order to predict the cytotoxic potentials of these compounds, quantitative structure-activity relationship studies were carried out using the methods of quantum chemistry. Five Quantitative Structure Activity Relationship (QSAR) models were obtained from the determined quantum descriptors and the different activities. The models present the following statistical indicators: regression correlation coefficient R2 = 0.986 - 0.905, standard deviation S = 0.516 - 0.153, Fischer test F = 106.718 - 14.220, correlation coefficient of cross-validation = 0.985- 0.895 and = 0.010 - 0.001. The statistical characteristics of the established QSAR models satisfy the acceptance and external validation criteria, thereby accrediting their good performance. The models developed show that the variation of the free enthalpy of reaction , the dipole moment μ and the charge of the ligand in the complex Ql, are the explanatory and predictive quantum descriptors correlated with the values of the anti-cancer activity of the studied complexes. Moreover, the charge of the ligand is the priority descriptor for the prediction of the cytotoxicity of the compounds studied. Furthermore, QSAR models developed are statistically significant and predictive, and could be used for the design and synthesis of new anti-cancer molecules.展开更多
Optimized calculations of 75 PCDDs and their parent DD were carded out at the B3LYP/6-31G＊ level by density functional theory （DFT） method. The structural parameters were obtained and significant correlation betwee...Optimized calculations of 75 PCDDs and their parent DD were carded out at the B3LYP/6-31G＊ level by density functional theory （DFT） method. The structural parameters were obtained and significant correlation between the C1 substitution position and some structural parameters was found. Consequently, the number of C1 substitution positions was taken as theoretical descriptors to establish two novel QSPR models for predicting lgKow and -lgSw of all PCDD congeners. The two models achieved in this work contain two variables （Na and Nβ）, of which r = 0.9312, 0.9965 and SD = 0.27, 0.12 respectively, and t values are all large. The variation inflation factors （VIF） of variables in the two models herein are both less than 5.0, suggesting high accuracy of the lgKow and -lgSw predicting models, and the results of cross-validation test also show that the two models exhibit optimum stability and good predictive power. By comparison, the correlation and predictive ability of the present work are more advantageous than those obtained using semi-empirical AM1 and GC-RI methods.展开更多
Optimized calculations of 209 polychlorinated diphenyl ethers （PCDEs） and diphenyl ethers were carried out at the B3LYP/6-31G^＊ level with the Gaussian 98 program. Based on the theoretical linear solvation energy r...Optimized calculations of 209 polychlorinated diphenyl ethers （PCDEs） and diphenyl ethers were carried out at the B3LYP/6-31G^＊ level with the Gaussian 98 program. Based on the theoretical linear solvation energy relationship （TLSER） model, the obtained structural parameters were taken as theoretical descriptors to establish the novel QSPR model for predicting aqueous solubility （-lgSw） of PCDEs. The model obtained in this work contains two variables： mean molecular polarizability （a） and the most positive partial charge on a hydrogen atom （qH^＋）, of which RE = 0.9606 and SD = 0.32. And the results of cross-validation test also show that the model exhibits optimum stability and better predictive power. Moreover, the predictive power of the new model is better than that of MCIs method.展开更多
Sodium azide is a widely used inorganic compound. Besides the commonly used method of ＂Wislicenus process＂ which uses ammonia, nitrous and sodium as materials, the hydrazine hydrate route is also employed for the pr...Sodium azide is a widely used inorganic compound. Besides the commonly used method of ＂Wislicenus process＂ which uses ammonia, nitrous and sodium as materials, the hydrazine hydrate route is also employed for the preparation of sodium azide particularly in laboratory. However, because many species are involved in the reaction system, the reaction details for the hydrazine hydrate route are still unclear. A comprehensive understanding of the reaction mechanism may provide meaningful help for optimizing the production process. In this work, the reaction mechanism for the synthesis of sodium azide by hydrazine hydrate route has been studied using density function theory（DFT） method. On the basis of our calculations, the reaction details, including the energetics of ten elementary steps, the structures of intermediates and transition states as well as the influence of inorganic acids and alcohols, were illuminated at the atomistic level. Both the two steps, the generation of key intermediate（NH2-NH-NO） and the trans-cistransformation of NH2-NH-NO, are suggested to be the possible rate-limiting step, corresponding to the energy barriers of 20.3 and 22.7 kcal/mol, respectively. In the early reaction steps to generate NH2-NH-NO, the main role of sulphuric acid is to donate proton, which can be replaced by nitric acid or hydrochloric acid. From the energy point of view, isopropanol has similar reactivity as methanol and ethanol.展开更多
Many attempts have been made to control the regioselectivity for olefin poly- merization by varying the structures of ligands in catalysts. The regioselectivity of propylene polymerization was investigated by replacin...Many attempts have been made to control the regioselectivity for olefin poly- merization by varying the structures of ligands in catalysts. The regioselectivity of propylene polymerization was investigated by replacing a nitrogen atom in the Pd(II) diimine catalyst with an oxygen atom from density functional theory method at the B3LYP/LANL2DZ level. The results show that the 1,2-insertion becomes a rival mechanism to the 2,1-insertion when the nitrogen atom is replaced by the oxygen atom leading to an asymmetric environment in the catalyst, and that the steric effect in the asymmetrical catalyst plays an important part in the polymerization. The insertion barrier from 2-O is much higher than that from 2-N. A pyramid transition state was characterized for the catalyst to convert 2-O back to 2-N through internal rotation. The propylene prefers to coordinate at the opposite side of O in the catalyst. This is the driving force for the internal rotation. The results are significant for isotactic and syndiotactic polymerization.展开更多
Orthogonal frequency division multiplexing(OFDM) is an attractive technique to realize high data rate in light emitting diodes(LEDs)-based visible light communication(VLC). However, high peak-to-average power ratio(PA...Orthogonal frequency division multiplexing(OFDM) is an attractive technique to realize high data rate in light emitting diodes(LEDs)-based visible light communication(VLC). However, high peak-to-average power ratio(PAPR) of OFDM makes VLC-OFDM very sensitive to the nonlinearity of LEDs. In this paper, the discrete Fourier transform-spread(DFT-spread) combined with clipping method is proposed to reduce the PAPR of OFDM signal in VLC system. Combining simulation with experiment, a performance comparison is made among conventional OFDM, DFT-spread-OFDM, and clipped DFT-spread-OFDM with different clipping ratios(CRs) in a single LED-based VLC system. The experimental results show that the proposed clipped DFT-spread-OFDM method can effectively improve the system performance compared with the other two methods. At the optimum signal peak-to-peak(PTP) value, by using the clipped DFT-spread-OFDM scheme with CR at 8 dB, the bit error rate(BER) of the system can be reduced from 0.003 7 to 0.000 287.展开更多
调制解调法是一种常用的微弱信号检测方法,高精度、低复杂度的解调方法的实现对于调制解调法的应用具有重要的意义.传统坐标旋转数字计算(coordinate rotation digital computer,CORDIC)算法具有占用资源多,需要缩放因子补偿等问题.因...调制解调法是一种常用的微弱信号检测方法,高精度、低复杂度的解调方法的实现对于调制解调法的应用具有重要的意义.传统坐标旋转数字计算(coordinate rotation digital computer,CORDIC)算法具有占用资源多,需要缩放因子补偿等问题.因此设计并实现了一种基于改进CORDIC算法的离散傅里叶变换(discrete Fourier transform,DFT)解调方法用于微弱信号的检测.首先改进了传统的CORDIC算法用于正余弦函数值的计算,该方法不仅免除了缩放因子,而且不需要进行旋转角度的判断,降低了算法的资源占用;然后基于该CORDIC算法设计了DFT解调算法,避免了乘法器与大量查找表的使用.最终仿真结果表明,设计的DFT解调方法在整周期采样的情况下能够实现对调制信号的高精度解调,并且具备良好的抗噪声性能,能够满足微弱信号检测的要求.展开更多
The TDDFT method is first applied in a series of tetra-nuclear transition metal clusters studies for nonlinear optical properties. The results indicate that the charge transfer inside the metal core [MCu3X4] (M=W, Mo...The TDDFT method is first applied in a series of tetra-nuclear transition metal clusters studies for nonlinear optical properties. The results indicate that the charge transfer inside the metal core [MCu3X4] (M=W, Mo; X=S, O, Cl, Se, Br) makes contribution to the optical nonlinearity. It is possible to enhance the hyperpolarizability by substituting the ligands of the clusters.展开更多
提出了一种近似重构、过采样DFT调制滤波器组的设计方法。根据滤波器组的系统失真和输出混迭方面的要求,构造一个简单的目标函数,并采用等纹波法优化设计原型滤波器。与现有方法相比,该设计方法将复杂的非线性优化问题转化为对单一参数...提出了一种近似重构、过采样DFT调制滤波器组的设计方法。根据滤波器组的系统失真和输出混迭方面的要求,构造一个简单的目标函数,并采用等纹波法优化设计原型滤波器。与现有方法相比,该设计方法将复杂的非线性优化问题转化为对单一参数的选取,简化了设计过程,并且可在满足DFT调制滤波器组设计准则的条件下使得通带范围内误差逼近最小。利用加权叠接相加(Weighted Overlap and Add,WOLA)的快速实现结构,使整个系统更加高效、易行,可用于助听器语音信号分频带处理与综合。展开更多
文摘A series of ruthenium azopyridine complexes have recently been investigated due to their potential cytotoxic activities against renal cancer (A498), lung cancer (H226), ovarian cancer (IGROV), breast cancer (MCF-7) and colon cancer (WIDR). Thus, in order to predict the cytotoxic potentials of these compounds, quantitative structure-activity relationship studies were carried out using the methods of quantum chemistry. Five Quantitative Structure Activity Relationship (QSAR) models were obtained from the determined quantum descriptors and the different activities. The models present the following statistical indicators: regression correlation coefficient R2 = 0.986 - 0.905, standard deviation S = 0.516 - 0.153, Fischer test F = 106.718 - 14.220, correlation coefficient of cross-validation = 0.985- 0.895 and = 0.010 - 0.001. The statistical characteristics of the established QSAR models satisfy the acceptance and external validation criteria, thereby accrediting their good performance. The models developed show that the variation of the free enthalpy of reaction , the dipole moment μ and the charge of the ligand in the complex Ql, are the explanatory and predictive quantum descriptors correlated with the values of the anti-cancer activity of the studied complexes. Moreover, the charge of the ligand is the priority descriptor for the prediction of the cytotoxicity of the compounds studied. Furthermore, QSAR models developed are statistically significant and predictive, and could be used for the design and synthesis of new anti-cancer molecules.
基金This work was supported by the National Natural Science Foundation of China (No. 20737001)(2003CB415002)China Postdoctoral Science Foundation (No. 2003033486)
文摘Optimized calculations of 75 PCDDs and their parent DD were carded out at the B3LYP/6-31G＊ level by density functional theory （DFT） method. The structural parameters were obtained and significant correlation between the C1 substitution position and some structural parameters was found. Consequently, the number of C1 substitution positions was taken as theoretical descriptors to establish two novel QSPR models for predicting lgKow and -lgSw of all PCDD congeners. The two models achieved in this work contain two variables （Na and Nβ）, of which r = 0.9312, 0.9965 and SD = 0.27, 0.12 respectively, and t values are all large. The variation inflation factors （VIF） of variables in the two models herein are both less than 5.0, suggesting high accuracy of the lgKow and -lgSw predicting models, and the results of cross-validation test also show that the two models exhibit optimum stability and good predictive power. By comparison, the correlation and predictive ability of the present work are more advantageous than those obtained using semi-empirical AM1 and GC-RI methods.
基金funded by the 973 National Basic Research Program of China (2003CB415002)China Postdoctoral Science Foundation (No. 2003033486)
文摘Optimized calculations of 209 polychlorinated diphenyl ethers （PCDEs） and diphenyl ethers were carried out at the B3LYP/6-31G^＊ level with the Gaussian 98 program. Based on the theoretical linear solvation energy relationship （TLSER） model, the obtained structural parameters were taken as theoretical descriptors to establish the novel QSPR model for predicting aqueous solubility （-lgSw） of PCDEs. The model obtained in this work contains two variables： mean molecular polarizability （a） and the most positive partial charge on a hydrogen atom （qH^＋）, of which RE = 0.9606 and SD = 0.32. And the results of cross-validation test also show that the model exhibits optimum stability and better predictive power. Moreover, the predictive power of the new model is better than that of MCIs method.
基金supported by the National Natural Science Foundation of China(21773138)
文摘Sodium azide is a widely used inorganic compound. Besides the commonly used method of ＂Wislicenus process＂ which uses ammonia, nitrous and sodium as materials, the hydrazine hydrate route is also employed for the preparation of sodium azide particularly in laboratory. However, because many species are involved in the reaction system, the reaction details for the hydrazine hydrate route are still unclear. A comprehensive understanding of the reaction mechanism may provide meaningful help for optimizing the production process. In this work, the reaction mechanism for the synthesis of sodium azide by hydrazine hydrate route has been studied using density function theory（DFT） method. On the basis of our calculations, the reaction details, including the energetics of ten elementary steps, the structures of intermediates and transition states as well as the influence of inorganic acids and alcohols, were illuminated at the atomistic level. Both the two steps, the generation of key intermediate（NH2-NH-NO） and the trans-cistransformation of NH2-NH-NO, are suggested to be the possible rate-limiting step, corresponding to the energy barriers of 20.3 and 22.7 kcal/mol, respectively. In the early reaction steps to generate NH2-NH-NO, the main role of sulphuric acid is to donate proton, which can be replaced by nitric acid or hydrochloric acid. From the energy point of view, isopropanol has similar reactivity as methanol and ethanol.
基金This work was supported by the Natural Science Foundation of Heilongjiang Province (No. B0313) and Research Foundation of China University of Mining and Technology
文摘Many attempts have been made to control the regioselectivity for olefin poly- merization by varying the structures of ligands in catalysts. The regioselectivity of propylene polymerization was investigated by replacing a nitrogen atom in the Pd(II) diimine catalyst with an oxygen atom from density functional theory method at the B3LYP/LANL2DZ level. The results show that the 1,2-insertion becomes a rival mechanism to the 2,1-insertion when the nitrogen atom is replaced by the oxygen atom leading to an asymmetric environment in the catalyst, and that the steric effect in the asymmetrical catalyst plays an important part in the polymerization. The insertion barrier from 2-O is much higher than that from 2-N. A pyramid transition state was characterized for the catalyst to convert 2-O back to 2-N through internal rotation. The propylene prefers to coordinate at the opposite side of O in the catalyst. This is the driving force for the internal rotation. The results are significant for isotactic and syndiotactic polymerization.
文摘Orthogonal frequency division multiplexing(OFDM) is an attractive technique to realize high data rate in light emitting diodes(LEDs)-based visible light communication(VLC). However, high peak-to-average power ratio(PAPR) of OFDM makes VLC-OFDM very sensitive to the nonlinearity of LEDs. In this paper, the discrete Fourier transform-spread(DFT-spread) combined with clipping method is proposed to reduce the PAPR of OFDM signal in VLC system. Combining simulation with experiment, a performance comparison is made among conventional OFDM, DFT-spread-OFDM, and clipped DFT-spread-OFDM with different clipping ratios(CRs) in a single LED-based VLC system. The experimental results show that the proposed clipped DFT-spread-OFDM method can effectively improve the system performance compared with the other two methods. At the optimum signal peak-to-peak(PTP) value, by using the clipped DFT-spread-OFDM scheme with CR at 8 dB, the bit error rate(BER) of the system can be reduced from 0.003 7 to 0.000 287.
文摘The TDDFT method is first applied in a series of tetra-nuclear transition metal clusters studies for nonlinear optical properties. The results indicate that the charge transfer inside the metal core [MCu3X4] (M=W, Mo; X=S, O, Cl, Se, Br) makes contribution to the optical nonlinearity. It is possible to enhance the hyperpolarizability by substituting the ligands of the clusters.
文摘提出了一种近似重构、过采样DFT调制滤波器组的设计方法。根据滤波器组的系统失真和输出混迭方面的要求,构造一个简单的目标函数,并采用等纹波法优化设计原型滤波器。与现有方法相比,该设计方法将复杂的非线性优化问题转化为对单一参数的选取,简化了设计过程,并且可在满足DFT调制滤波器组设计准则的条件下使得通带范围内误差逼近最小。利用加权叠接相加(Weighted Overlap and Add,WOLA)的快速实现结构,使整个系统更加高效、易行,可用于助听器语音信号分频带处理与综合。
