On quantitative structure-activity relationships between hydrazine derivatives and β irradiation

On quantitative structure-activity relationships between hydrazine derivatives and β irradiation 1 2 first-author 2 2 2 1 corresp Corresponding author. E-mail address: liuof99@163.com Corresponding author. E-mail address: liuof99@163.com liuof99@163.com 2 2 Fundamental Science on Radioactive Geology and Exploration Technology Laboratory, East China University of Technology, NanChang 330013, China Fundamental Science on Radioactive Geology and Exploration Technology Laboratory, East China University of Technology, NanChang 330013, China China Institute of Atomic Energy, Beijing 102413, China China Institute of Atomic Energy, Beijing 102413, China In this study, solutions of hydrazine and its derivatives were irradiated using a pulsed electron beam to determine the half-reaction time of radiolysis. 3D structures of the hydrazine derivatives were optimized and their energies were calculated using density functional theory with the B3LYP method and 6-311+( 3d, 3p ) basis set. For the first time, the 3D quantitative structure-activity relationship (QSAR) equation describing the relationship between the hydrazine derivative structures and rate of radiolysis has been established using SPSS software. Pearson correlation analysis revealed a close correlation between the total energies of the molecules and half-reaction times. In the QSAR equation, Y = −7583.464 + 54.687 X 1 + 94333.586 X 2 , Y , X 1 , and X 2 are the half-reaction time, total energy of the molecule, and orbital transition energy, respectively. The significance levels of the regression coefficients were 0.006 and 0.031, i.e., both less than 0.05. Thus, this model fully explains the relationship between hydrazine derivatives and β radiolysis stability. The results show that the total energy of the molecule and orbital transition energy are the main factors that influence the β radiolysis stability of these hydrazine derivatives. Hydrazine derivatives β irradiation Radiolysis stability Quantitative structure-activity relationships 1 Introduction 1 Hydrazine and its derivatives, which are highly toxic and strong reducing agents, are miscible with water and soluble in most organic solvents. Hydrazine, methylhydrazine, 1,1-dimethylhydrazine, phenylhydrazine, 2-hydroxyethylhydrazine, and tert -butylhydrazine are the most common hydrazine derivatives. They are important chemical raw materials and widely used in polymers, metallic materials, metallurgy, printing and dyes, textiles, medicine, disease treatment, etc. [ 1 1 - 3 3 1-3 ]. In particular, they are used as propellants for altitude control engines in missiles, satellites, and the aerospace industry because they readily combust to produce hydrogen and nitrogen [ 4 4 - 6 6 4-6 ]. Owing to their strong reduction properties, they have been extensively studied in the Purex process as a support reducing stabilizer for the recovery of Pu(Ⅳ) using Fe(II), U(IV), hydroxylamine, and urea. They have also been considered as organic salt-free reduc tants for Pu(Ⅳ) and Np(Ⅵ) during the post-treatment of nuclear fuel [ 7 7 ]. Accordingly, significant research effort has been targeted at their application as support reducing agents or reducing agents for spent nuclear fuel reprocessing in recent years [ 8 8 ]. A significant amount of hydrazine derivatives are released into the environment as pollutants [ 9 9 - 12 12 9-12 ]. They are strong stimulants and may induce acute poisoning via injection, inhalation, skin poisoning, and gastrointestinal absorption or cause tumor growth. Thus, hydrazine derivatives are considered to be very harmful for living organisms and the environment. Once they are released to the environment, they can physically adsorb and interact chemically with the soil, resulting in a polluted environment that is difficult to reclaim. Some of the degradation products of hydrazine derivatives are more toxic that the derivatives themselves. Therefore, efficient wastewater disposal and decomposition treatment of effluent containing hydrazine derivatives is important. The stoichiometry, kinetics, and mechanisms of the decomposition of hydrazine and its derivatives have yet to be fully elucidated [ 13 13 ]. Currently, the following types of treatment methods for hydrazine compounds are used globally: (1) Physical methods, such as incineration, ion exchange, adsorption, etc., are simple to use but readily produce secondary pollution; also, the regeneration period and lifetime of the ion resin are limited. (2) Biodegradation, which includes activated sludge (microbial) and aquatic plant treatment, is an environmentally friendly method; however, it cannot be applied to non-industrial effluent because the pollutants could bioaccumulate in organisms and avoid fundamental degradation [ 14 14 ]. (3) Chemical oxidation methods, such as catalytic oxidation, electrolyzed oxidizing water (EOW) oxidation, and photocatalytic oxidation, etc. [ 15 15 ], quickly oxidize and remove the organic matter by destroying the organic molecular structure. These methods are suitable for industrial processes; however, they are restricted to wastewater with low pollutant concentrations. (4) Other new processing technologies, such as low temperature plasma technology [ 16 16 , 17 17 ], catalyzed supercritical water oxidation [ 18 18 , 19 19 ], Fenton oxidation, and membrane bioreactor treatment [ 20 20 ], have also been applied. Fenton’s method has been widely studied because of the high activity of hydroxyl radicals towards the oxidation and decomposition of a variety of organic substances that are typically difficult to oxidize. Radiation technology has been used in the environmental field [ 21 21 ], which is an important aspect of the peaceful use of atomic energy in the 21st century, as proposed by the International Atomic Energy Agency. Radiation technology is a non-polluting, inexpensive, simple, and efficient degradation method. The application of beta radiation technology to remove hydrazine pollutants should generate the target outcome with a lower energy consumption and at a faster rate. Hydrazine and its derivatives have been actively researched as support reducing stabilizers and novel salt free reductants; therefore, their stability under radiation exposure during the post-treatment process is important for the optimal selection of reducing agents for spent fuel reprocessing. The quantitative structure-activity relationships (QSAR) method [ 22 22 - 24 24 22-24 ] is widely used during the development of new medicines and is a well-recognized research method. However, it is rarely used in other fields, especially that of radiochemistry. In this study, five hydrazine derivatives, i.e., hydrazine hydrate, methylhydrazine, dimethylhydrazine, tert -butylhydrazine, and 2-hydroxyethylhydrazine, were irradiated using a pulsed electron beam. The data were then analyzed to establish the QSAR model. This investigation of the radiative stability of hydrazine and its derivatives under β radiolysis expands the fundamental knowledge on the radiochemistry of inorganic compounds and provides abundant theoretical evidence of the degradation of hydrazine. It also provides an important guideline for the degradation of hydrazine and its derivatives in spent nuclear fuel. 2 Source and structure of the target compound 1 2.1 Chemicals and equipment 2 All chemicals were of analytical grade and used without further purification. Hydrazine hydrate (85%) was purchased from Shanghai Hushi Laboratorial Equipment Co. Ltd. (China). tert -Butylhydrazine (98%) and 2-hydroxyethylhydrazine (95%) were purchased from Shanghai Macklin Biochemical Co. Ltd. (China). Methylhydrazine, dimethylhydrazine, and p -dimethylaminobenzaldehyde were purchased from Sinopharm Chemical Reagent Co. Ltd. (China). Ethanol, nitric acid, and methane sulfonic acid (MSA) were purchased from Beijing Chemical Works (China). A beta particle accelerator (2 MeV), ion chromatograph (CIC-100), ultraviolet spectrophotomer (Perkin Elmer Lamda 45), and automatic potentiometric titrator (Mettler-Toledo G20 compact titrator) were used during the experiment. The beta particle accelerator was rented from the Department of Nuclear Technology Applications in China Institute of Atomic Energy, and the required safety protection was provided. The ion chromatograph was purchased from Qingdao Sheng Han Chromatography Technology Co. Ltd. (China); a CS12A column was used as the cation column, and the baseline noise was stabilized at around 20 mV before detection. 2.2 Experimental method 2 There are a few published research papers on the stability of hydrazine and its derivatives under radiation. For example, a group at the National Institute of Atomic Energy researched their stability under γ radiation. However, γ rays are difficult to use because of their high energy and radiation dose, which makes them unsuitable for large-scale industrial applications. There is no suitable kinetic data regarding the β radiation stability of hydrazine and its derivatives. Therefore, in this paper, source data were obtained using experimental and computational methods. The initial solutions of hydrazine and its derivatives were diluted to 0.05 mol/L; then, 250 mL aliquots of the solutions were prepared and irradiated using a pulsed electron beam from a beta particle accelerator. The accelerator used a 30 mA current, 50 Hz frequency, 4 μs pulse width, and 0.25 KGy/s dose. Then, 0.1 mL samples of the irradiated solutions were extracted using a syringe after the following irradiation durations: 0, 0.5, 1, 2, 3, 4, 5, 6, 7, 9, 11, 13, 15, 18, and 21 min. 2.3 Analytic procedures 2 Using methane sulfonic acid as the eluent, the concentrations of the hydrazine, tert -butylhydrazine, 1,1-dimethylhydrazine, and 2-hydroxyethylhydrazine solutions were separately determined using ion chromatography. The concentration of methylhydrazine was determined using an ultraviolet visible spectrophotometer with the color rendering of p -dimethylaminobenzaldehyde. The concentrations of the irradiated solutions were determined after the following irradiation durations: 0, 0.5, 1, 2, 3, 4, 5, 6, 7, 9, 11, 13, 15, 18, and 21 min. Then, the kinetic data for the decomposition of the hydrazine derivatives under beta radiation were obtained. The half-reaction times of hydrazine and its derivatives under β-radiation are expressed by τ 50 , which is the time required for the compound to decompose to 50% of the original concentration: A smaller τ 50 value indicates a faster decomposition rate. The molecular formulas of various hydrazine derivatives and their τ 50 values are listed in Table 1 Table 1 . 1 1 Derivatives 1 1 τ 50 (s) 1 1 Hydrazine, N 2 H 4 1 1 8155.6 1 1 methyl hydrazine, CH 3 N 2 H 3 1 1 6689.2 1 1 1,1-dimethylhydrazine, (CH 3 ) 2 N 2 H 2 1 1 791.6 1 1 tert -butylhydrazine, (CH 3 ) 3 CHN 2 H 3 1 1 426.2 1 1 2-hydroxyethylhydrazine, HOCH 2 CH 2 N 2 H 3 1 1 204.5 3 Calculation methods 1 The initial structures of the hydrazine compounds were generated using ChemOffice software, and geometric pre-optimization was conducted using built-in molecular mechanics MM2 modules in Chem3D Ultra. The minimum energy conformation of the hydrazine derivative was obtained after optimization. Geometric optimization and energy calculations were conducted on a variety of target compounds by applying the density functional theory B3LYP method of the Gaussian 03 program package with a 6-311+( 3d, 3p ) basis set. The vibration frequencies calculated for all of the molecular structures did not have imaginary frequencies, which indicates that the configuration obtained from the calculation was the most stable. Using the HyperChem software package, calculations were conducted on the optimized molecules and the physicochemical parameters were obtained; these included the total energy ( E total ), highest occupied molecular orbital energy ( E HOMO ), lowest unoccupied molecular orbital energy ( E LUMO ), molecular orbital transition energy (Δ E ), molecular dipole moment ( μ ), hydrophobic parameter (log P ), molecular refractivity ( R ), molecular volume ( V ), molecular superficial area ( A ), molecular molar mass ( M ), molecular polarizability ( P ), and hydration energy ( HE ). Mathematical statistical software, SPSS, was applied to perform a correlation analysis and stepwise regression analysis on the τ 50 and physicochemical parameters of the selected hydrazine derivatives. Finally, a QSAR equation with sufficient correlation was obtained. The convergence precision of the quantum chemical calculations is a default value. 4 Results and discussion 1 4.1 3D stable molecular structures of the hydrazine compounds 2 Optimized geometric construction and frequency analysis of the hydrazine derivatives were conducted by adopting the density functional theory B3LYP method of the Gaussian 03 program package with the 6-311+( 3d, 3p ) basis set. No imaginary frequency occurred in the calculation results, indicating that they were reasonable and reliable. This also confirms that the most stable configuration was obtained. The optimized 3D structures are shown in Fig. 1 Fig. 1 . 4.2 Values of the quantum chemical parameters 2 The following parameter values were acquired from the quantum chemical calculations: E LUMO , E HOMO , Δ E (Δ E = E LUMO − E HOMO ), μ , and E total . In addition, the following parameters were obtained using the molecular simulation software, HyperChem: log P , R , V , molecular superficial area ( A - approx, G - grid), M , P , and HE . The degradation rates of hydrazine and its derivatives under β irradiation are expressed by τ 50 . The quantum parameter values are shown in Table 2 Table 2 . Units: E LUMO , E HOMO , Δ E , and E (a.u.), μ (Debye), M (amu), and HE (kcal/mol) 1 1   1 1 E HOMO 1 1 E LUMO 1 1 Δ E 1 1 E total 1 1 μ 1 1 log P 1 1 R 1 1 V 1 1 A 1 1 G 1 1 M 1 1 P 1 1 HE 1 1 hydrazine 1 1 -0.218 1 1 0.011 1 1 0.229 1 1 -111.912 1 1 0.000 1 1 -0.680 1 1 10.570 1 1 183.870 1 1 135.890 1 1 158.850 1 1 32.050 1 1 3.480 1 1 -21.860 1 1 methylhydrazine 1 1 -0.243 1 1 -0.002 1 1 0.241 1 1 -151.237 1 1 1.740 1 1 -0.460 1 1 14.280 1 1 239.450 1 1 143.590 1 1 190.220 1 1 46.070 1 1 5.310 1 1 -13.590 1 1 1,1-dimethylhydrazine 1 1 -0.203 1 1 -0.003 1 1 0.201 1 1 -190.554 1 1 0.564 1 1 -0.550 1 1 19.180 1 1 291.360 1 1 134.660 1 1 217.930 1 1 60.100 1 1 7.150 1 1 -.640 1 1 tert -butylhydrazine 1 1 -0.239 1 1 -0.004 1 1 0.235 1 1 -269.218 1 1 1.746 1 1 0.760 1 1 27.970 1 1 393.630 1 1 142.060 1 1 275.410 1 1 88.150 1 1 10.820 1 1 -4.730 1 1 2-hydroxyethylhydrazine 1 1 -0.247 1 1 -0.005 1 1 0.241 1 1 -265.806 1 1 1.183 1 1 -0.910 1 1 20.570 1 1 319.840 1 1 246.110 1 1 239.980 1 1 76.100 1 1 7.780 1 1 -17.450 4.3 Structure-performance equation for the hydrazine derivatives under β irradiation 2 Before a QSAR regression equation was established, the quantum chemical parameters adopted were applied for preprocessing. The Pearson correlation coefficient analysis parameters that were significantly related to the β irradiation half-reaction time were obtained to facilitate elucidation of the relationship between the parameters of each structure and the degradation rate of the target compound. Statistical software, SPSS, was applied to conduct a correlation analysis on the QSAR parameters to obtain the Pearson correlation coefficient matrix ( Table 3 Table 3 ). 1 1   1 1 τ 50 1 1 E HOMO 1 1 E LUMO 1 1 Δ E 1 1 E total 1 1 μ 1 1 log P 1 1 R 1 1 V 1 1 A 1 1 G 1 1 M 1 1 P 1 1 HE 1 1 τ 50 1 1 1 1 1 0.085 1 1 0.782 1 1 0.221 1 1 0.909 1 1 -0.338 1 1 -0.292 1 1 -0.883 1 1 -0.866 1 1 -0.438 1 1 -0.891 1 1 -0.906 1 1 -0.863 1 1 -0.632 1 1 E HOMO 1 1 0.085 1 1 1 1 1 0.448 1 1 -0.933 1 1 0.462 1 1 -0.762 1 1 -0.177 1 1 -0.339 1 1 -0.288 1 1 -0.564 1 1 -0.369 1 1 -0.401 1 1 -0.310 1 1 -0.350 1 1 E LUMO 1 1 0.782 1 1 0.448 1 1 1 1 1 -0.095 1 1 0.798 1 1 -0.770 1 1 -0.262 1 1 -0.782 1 1 -0.735 1 1 -0.425 1 1 -0.793 1 1 -0.795 1 1 -0.756 1 1 -0.572 1 1 Δ E 1 1 0.221 1 1 -0.933 1 1 -0.095 1 1 1 1 1 -0.192 1 1 0.538 1 1 0.091 1 1 0.062 1 1 0.024 1 1 0.456 1 1 0.091 1 1 0.126 1 1 0.040 1 1 -0.620 1 1 E total 1 1 0.909 1 1 0.462 1 1 0.798 1 1 -0.192 1 1 1 1 1 -0.569 1 1 -0.419 1 1 -0.944 1 1 -0.919 1 1 -0.569 1 1 -0.960 1 1 -0.984 1 1 -0.920 1 1 -0.403 1 1 μ 1 1 -0.338 1 1 -0.762 1 1 -0.770 1 1 0.538 1 1 -0.569 1 1 1 1 1 0.536 1 1 0.627 1 1 0.593 1 1 0.173 1 1 0.629 1 1 0.605 1 1 0.621 1 1 0.301 1 1 log P 1 1 -0.292 1 1 -0.177 1 1 -0.262 1 1 0.091 1 1 -0.419 1 1 0.536 1 1 1 1 1 0.665 1 1 0.712 1 1 -0.425 1 1 0.631 1 1 0.562 1 1 0.710 1 1 0.535 1 1 R 1 1 -0.883 1 1 -0.339 1 1 -0.782 1 1 0.062 1 1 -0.944 1 1 0.627 1 1 0.665 1 1 1 1 1 0.996 1 1 0.266 1 1 0.998 1 1 0.988 1 1 0.998 1 1 0.620 1 1 V 1 1 -0.866 1 1 -0.288 1 1 -0.735 1 1 0.024 1 1 -0.919 1 1 0.593 1 1 0.712 1 1 0.996 1 1 1 1 1 0.198 1 1 0.991 1 1 0.974 1 1 0.999 1 1 0.644 1 1 A 1 1 -0.438 1 1 -0.564 1 1 -0.425 1 1 0.456 1 1 -0.569 1 1 0.173 1 1 -0.425 1 1 0.266 1 1 0.198 1 1 1 1 1 0.319 1 1 0.412 1 1 0.203 1 1 -0.369 1 1 G 1 1 -0.891 1 1 -0.369 1 1 -0.793 1 1 0.091 1 1 -0.960 1 1 0.629 1 1 0.631 1 1 0.998 1 1 0.991 1 1 0.319 1 1 1 1 1 0.995 1 1 0.993 1 1 0.586 1 1 M 1 1 -0.906 1 1 -0.401 1 1 -0.795 1 1 0.126 1 1 -0.984 1 1 0.605 1 1 0.562 1 1 0.988 1 1 0.974 1 1 0.412 1 1 0.995 1 1 1 1 1 0.976 1 1 0.523 1 1 P 1 1 -0.863 1 1 -0.310 1 1 -0.756 1 1 0.040 1 1 -0.920 1 1 0.621 1 1 0.710 1 1 0.998 1 1 0.999 1 1 0.203 1 1 0.993 1 1 0.976 1 1 1 1 1 0.646 1 1 HE 1 1 -0.632 1 1 0.350 1 1 -0.572 1 1 -0.620 1 1 -0.733 1 1 -0.403 1 1 0.301 1 1 0.535 1 1 0.620 1 1 0.644 1 1 -0.369 1 1 0.523 1 1 0.646 1 1 1 It is evident from the data in Table 3 Table 3 that the correlations between τ 50 and E total and M are significant. G , R , V , E LUMO , HE , A , μ , P , Δ E , and log P also had strong correlations with τ 50 . However, there was no significant correlation between E HOMO and τ 50 . The Pearson correlation analysis shows that there is a close relationship between the total energy of the molecules and τ 50 of the hydrazine compounds radiolysis reaction under beta irradiation; their relationship diagram was established, as depicted in Fig. 2 Fig. 2 . In Fig. 2 Fig. 2 , a relationship between the E total and τ 50 of the hydrazine derivatives hydrolysis reaction under beta irradiation is slightly evident. In general, τ 50 is positively correlated with E total ; however, the correlation cannot be defined using a mathematical relationship. Accordingly, we used a multiple linear stepwise regression method to analyze the data. 4.4 QSAR equation for the hydrazine derivatives under β irradiation 2 The QSAR equation for the hydrazine derivatives (i.e., hydrazine, methylhydrazine, 1,1-dimethylhydrazine, tert -butylhydrazine, and 2-hydroxyethylhydrazin) under β irradiation was established using a multiple linear stepwise regression method, and the results are shown in Tables 4 Tables 4 , 5 5 , 6 6 and 7 7 . a Dependent variable: half-reaction time 1 1 Model 1 1 Variables entered 1 1 Variables removed 1 1 method 1 1 1 1 1 Molecule total energy 1 1   1 1 stepwise 1 1 2 1 1 Orbital transition energy 1 1   1 1 stepwise a Predictors: (Constant): molecule total energy b Predictors: (Constant): molecule total energy, orbit transition energy c Dependent variable: half-reaction time 1 1 Model 1 1 R 1 1 R square 1 1 Adjusted R square 1 1 Standard error of the estimate 1 1 1 1 1 0.909 a 1 1 0.827 1 1 0.769 1 1 1848.089752 1 1 2 1 1 0.995 b 1 1 0.989 1 1 0.979 1 1 559.650556 a Predictors: (Constant): molecule total energy b Predictors: (Constant): molecule total energy, orbital transition energy c Dependent variable: half-reaction time 1 1 Model 1 1   1 1 Sum of squares 1 1 d f 1 1 Mean square 1 1 F 1 1 Significance 1 1 1 1 1 Regression 1 1 4.894×10 7 1 1 1 1 1 4.894×10 7 1 1 14.329 1 1 0.032 a 1 1   1 1 Residual 1 1 1.025×10 7 1 1 3 1 1 3.415×10 6 1 1   1 1   1 1   1 1 Total 1 1 5.918×10 7 1 1 4 1 1   1 1   1 1   1 1 2 1 1 Residual 1 1 5.856×10 7 1 1 2 1 1 2.928×10 7 1 1 93.481 1 1 0.011 b 1 1   1 1 Residual 1 1 6.264×10 5 1 1 2 1 1 3.132×10 5 1 1   1 1   1 1   1 1 Total 1 1 5.918×10 7 1 1 4 1 1   1 1   1 1   a Dependent variable: half-reaction time 1 1 Model 1 1   2 1 Unstandardized Coefficients 1 1 Standardized coefficients 1 1 t 1 1 Significance 1 1   1 1   1 1 B 1 1 standard error 1 1 Beta 1 1   1 1   1 1 1 1 1 (Constant) 1 1 13205.114 1 1 2755.880 1 1   1 1 4.792 1 1 0.017 1 1   1 1 total energy 1 1 50.326 1 1 13.295 1 1 0.909 1 1 3.785 1 1 0.032 1 1 2 1 1 (Constant) 1 1 -7583.464 1 1 3842.799 1 1   1 1 -1.973 1 1 0.187 1 1   1 1 Molecule total energy 1 1 54.687 1 1 4.102 1 1 0.988 1 1 13.331 1 1 0.006 1 1   1 1 Orbital transition energy 1 1 94333.586 1 1 17021.516 1 1 0.411 1 1 5.542 1 1 0.031 The stepwise regression analysis results suggest the following: 1) Significant correlation exists between E total and τ 50 as well as E total and Δ E , as shown in Tables 4 Tables 4 and 5 5 . The square root of the determination coefficient, determination coefficient, and adjusted determination coefficient were 0.995, 0.989, and 0.979, respectively; these values indicate that the equations could account for 97.9% of the change in the τ 50 and that the correlations between independent and dependent variable are evident. (2) The square of the equation, residual sum of the squares, total sum of the squares, F-statistics value, and significance were 5.858 × 10 7 , 0.955, 6.264 × 10 5 , 93.481, and 0.011 < 0.05, respectively, indicating that a significant linear relationship exists between the dependent and independent variables. (3) From Table 7 Table 7 , it is evident that the QSAR equation for the hydrazine derivatives and τ 50 of the hydrazine derivatives hydrolysis reaction under beta radiation was Y = −7583.464 + 54.687 X 1 + 94333.586 X 2 , where X 1 and X 2 represent E total and Δ E , respectively. The significance levels of the regression coefficients are 0.006 and 0.031; these values are less than 0.05. This model fully represents the relationship between the hydrazine derivatives and β radiolysis stability. 4.5 The relationship between the hydrazine derivative structure and half-reaction time for β irradiation 2 In the structural activity equation, the τ 50 for hydrazine compound radiolysis relates closely with E total and Δ E . A diagram of their relationship is shown in Fig. 3 Fig. 3 . The analysis results indicate the following: 1) The relationship between the structure of the hydrazine derivative and reaction time can be described quantitatively by the QSAR equation even for complex hydrazine derivative structures. 2) The decomposition rate under β irradiation and structure of the hydrazine derivatives are negatively correlated and can be described quantitatively by E total and Δ E . 3) The relationship between the decomposition rate under β irradiation and structure of the hydrazine derivatives can be described quantitatively by the QSAR equation, which simplifies the complex problem and provides direction for the subsequent study of hydrazine and its derivatives. 5 Conclusion 1 In this work, the relationship between the structure of hydrazine derivatives and β radiolysis stability was studied resulting in a quantitative structural activity relationship equation. The most stable configurations of the five hydrazine derivatives was obtained by geometrical optimization and energy calculations. The relationships between the half lifetimes of radiolysis and structural parameters of the hydrazine derivatives were analyzed using the Pearson correlation coefficient, and there was significant correlation with the total energy and molecular mass. There was also strong correlation with the molecular superficial area, molecular refractivity, molecular volume, lowest unoccupied molecular orbital energy, orbital transition energy, etc. The 3D-QSAR structure equations between the structure and rate of radiolysis were also established using SPSS software. According to the model equation, the total energy of the molecule and orbital transition energy are the main factors that affect the stability of hydrazine derivatives under beta radiolysis, and the correlation is negative. 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(in Chinese) doi: 10.11889/j.0253-3219.2016.hjs.39.080302 http://doi.org/10.11889/j.0253-3219.2016.hjs.39.080302 The investigation of the quantitative structure-activity relationships between the structure of hydrazine derivatives and the reduction of Pu(IV) 10.1007/s41365-018-0409-x 2017-05-19 2017-07-19 2017-08-20 2018-03-30 2018-05-01 2021-04-11 © China Science Publishing & Media Ltd. (Science Press), Shanghai Institute of Applied Physics, the Chinese Academy of Sciences, ChineseNuclear Society and Springer Nature Singapore Pte Ltd. 2018 This is a post-peer-review, pre-copyedit version of an article published in Nuclear Science and Techniques. The final authenticated version is available online at: http://dx.doi.org/10.1007/s41365-018-0409-x http://dx.doi.org/10.1007/s41365-018-0409-x . 2018 Nuclear Science and Techniques 05 29