Syntheses,Crystal Structures,and Thermal Properties of Energetic Semicarbazide Salt,Manganese(II) Salt,and Coordination Compound of 3,5‐Dinitrobenzoic Acid

Nitro compounds have been actively researched as driven by their potential to be high‐performing energetic materials. Herein, three new nitro compounds including semicarbazide 3,5‐dinitrobenzoate, (SCZ)(DNBA), manganese 3,5‐dinitrobenzoate dihydrate, [Mn(DNBA)₂(H₂O)₂]_n, and bis(semicarbazide) manganese(II) 3,5‐dinitrobenzoate, Mn(SCZ)₂(DNBA)₂, were synthesized and characterized by elemental analysis, IR spectroscopy, and single‐crystal X‐ray diffraction analysis. The results indicated that the above mentioned compounds are ionic, polymeric, and molecular in nature, respectively. Moreover, their thermal decomposition properties were assessed by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Their non‐isothermal reaction kinetics parameters, critical temperature of thermal explosion (T_bp), entropy of activation (ΔS^≠), enthalpy of activation (ΔH^≠), and free energy of activation (ΔG^≠) of the exothermic decomposition process were also calculated. Results suggest that there was a relationship between the structure and thermal stability.     

Synthesis,Crystal Structure,Thermal and Explosive Properties of [Cd(SCZ)3(H2O)](PA)2·3H2O (SCZ = Semicarbazide,PA = Picrate)

The heptacoordinate transition metal coordination compound [Cd(SCZ)₃(H₂O)](PA)₂ · 3H₂O ( 1 ) with the ligand semicarbazide (SCZ) and the counteranion picrate (PA) was synthesized and characterized by elemental analysis and FTIR spectroscopy. Single‐crystal X‐ray diffraction analysis revealed that 1 crystallizes in the monoclinic space group P21/c. The Cd²⁺ ion is heptacoordinated by three SCZ groups and a water molecule. SCZ presents typical bidentate coordination modes. The thermal decomposition mechanism of 1 was studied by differential scanning calorimetry (DSC), which revealed that complex 1 exhibits three small endothermic and two large exothermic processes. The non‐isothermal kinetics parameters were calculated by the Kissinger's method and Ozawa‐Doyle's method, respectively. The heat of combustion was measured by oxygen bomb calorimetry. The enthalpy of formation, the critical temperature of thermal explosion, the entropy of activation (ΔS^≠), the enthalpy of activation (ΔH^≠), and the free energy of activation (ΔG^≠) were also calculated. Sensitivity tests revealed that 1 is insensitive to mechanical stimuli.     

Synthesis,crystal structures and thermal stabilities of zinc coordination polymers containing the 3-hydrazino-4-amino-1,2,4-triazole ligand

Two zinc coordination polymers, {[Zn(HATr)₂](NO₃)₂}_n (1) and {[Zn₂(HATr)₄](ZnCl₄)(NO₃)₂·H₂O}_n (2), were synthesized from reactions of 3-hydrazino-4-amino-1,2,4-triazole dihydrochloride (HATr·2HCl) with Zn(NO₃)₂. The polymers were characterized by single-crystal X-ray diffraction, Fourier transform infrared spectroscopy (FTIR), elemental analysis, and differential scanning calorimetry. The crystal structures revealed that 1 and 2 have 1-D-chain structures, which were further assembled to form 3-D-frameworks by hydrogen bonds. Thermal analyses showed that these two compounds have thermal stability up to 280 °C. The energies of combustion, enthalpies of formation, critical temperatures of thermal explosion, entropies of activation (ΔS^≠), enthalpies of activation (ΔH^≠), and free energies of activation (ΔG^≠) were also measured and calculated. Furthermore, the sensitivities of 1 and 2 toward impact, friction, and static were determined, which revealed that 1 and 2 were less sensitive than Ni(N₂H₄)₃(NO₃)₂.     

Preparation,Crystal Structure,and Thermal Decomposition of the Intriguing Five‐coordinated Compound [Cu(IMI)4Cl]Cl (IMI = Imidazole)

The intriguing multi‐ligand compound [Cu(IMI)₄Cl]Cl ( 1 ) with the ligand imidazole (IMI) was synthesized and characterized by elemental analysis and FT‐IR spectroscopy. The crystal structure was determined by X‐ray single crystal diffraction and the crystallographic data showed that the compound belongs to the monoclinic P2₁/n space group [α = 8.847(2) Å, b = 13.210(3) Å, c = 13.870(3) Å, and β = 90.164(3)°]. Furthermore, the Cu^II ion is five‐coordinated by four nitrogen atoms from four imidazole ligands and a chlorine atom. The thermal decomposition mechanism was determined based on differential scanning calorimetry (DSC) and thermogravimetric (TG‐DTG) analysis. The non‐isothermal kinetics parameters were calculated by the Kissinger's method and Ozawa's method, respectively. The energy of combustion, enthalpy of formation, critical temperature of thermal explosion, entropy of activation (ΔS^≠), enthalpy of activation (ΔH^≠), and free energy of activation (ΔG^≠) were measured and calculated.     

Non-isothermal Kinetics of the First-stage Decomposition Reaction of the Complex of Terbium p-Methylbenzoate with 1,10-Phenanthroline

The thermal behavior of Tb₂ (p‐MBA)₆(phen)₂ (p‐MBA=p‐methylbenzoate; phen=1,10‐phenanthroline) in a static air atmosphere was investigated by TG‐DTG, SEM and IR techniques. The thermal decomposition of the Tb₂(p‐MBA)₆(phen)₂ occurred in three consecutive stages at T_P of 354, 457 and 595 °C. By Malek method, RO (n<1) was defined as kinetic model for the first‐step thermal decomposition. The activation energy (E) of this step is 170.21 kJ·mol^‐1, the enthalpy of activation (ΔH^≠) 164.98 kJ·mol^‐1, the Gibbs free energy of activation (ΔG^≠) 145.04 kJ·mol^‐1, the entropy of activation (ΔS^≠) 31.77 J·mol^‐1·K^‐1, and the pre‐exponential factor (A) 10^15.21 s^‐1.     

Preparation,crystal structure,and thermal decomposition of an azide energetic compound [Cd(IMI)2(N3)2]n (IMI = imidazole)

Cadmium(II) imidazole (IMI) azide [Cd(IMI)₂(N₃)₂]_n (1) was synthesized using imidazole and azide, and was characterized by the elemental analysis and FTIR spectrum. The crystal structure was determined by X-ray single crystal diffraction, and the crystallographic data show that the crystal belongs to orthorhombic, Pba2 space group, α?=?10.780(4) Å, b?=?13.529(5) Å, and c?=?3.6415(12) Å. Its crystal density is 2.080?g·cm^–3. Cd(II) is a six-coordinate with six nitrogens from four imidazoles and two azides with μ–1,1 coordination. The thermal decomposition mechanism was determined based on differential scanning calorimetry (DSC) and thermogravimetry-derivative thermogravimetry (TG-DTG) analysis, and the kinetic parameters of the first exothermic process were studied using Kissinger’s method and Ozawa’s method, respectively. The energy of combustion, enthalpy of formation, critical temperature of thermal explosion, entropy of activation (ΔS ^≠), enthalpy of activation (ΔH ^≠), and free energy of activation (ΔG ^≠) were measured and calculated. In the end, impact sensitivity was also determined by standard method.     

Synthesis,structure, and thermal decomposition of two copper coordination compounds [Cu(DAT)2(PA)2] and [Cu(DAT)2(HTNR)2] with nitrogen rich 1,5-diaminotetrazole (DAT)

Both [Cu(DAT)₂(PA)₂] (1) and [Cu(DAT)₂(HTNR)₂] (2) were prepared from 1,5-diaminotetrazole (DAT) and copper trinitrophenol, 1 for picrate (PA) and 2 for styphnate acid (2,4,6-trinitro resorcinol, TNR), and were characterized by elemental analysis, FT-IR spectroscopy, and single crystal X-ray diffraction. The space group of these compounds is P2₁/c (monoclinic). The lattice parameters are similar [a = 11.405(3) Å, b = 14.867(3) Å, c = 8.099(2) Å for 1 and a = 12.262(3) Å, b = 14.900(3) Å, c = 7.243(2) Å for 2], except the β = 106.257(3)° in 1 and β = 92.989(4)° in 2. Both have extended structures due to hydrogen bonds, but there are some differences because of the ligands induced effect. Differential scanning calorimetry analysis shows that two exothermic processes take place in both complexes, the first peak temperatures are 488.2 K for 1 and 519.2 K for 2. The kinetic parameters of the first exothermic process were studied by using Kissinger’s method and Ozawa’s method, in which the enthalpy of formation (?7346 and ?5706 kJ M^?1), critical temperature of thermal explosion (475.0 and 515.8 K), entropy of activation (ΔS^≠), enthalpy of activation (ΔH^≠), and free energy of activation (ΔG^≠) were calculated and obtained as ?117.25 J K^?1 M^?1, 140.64 kJ M^?1, 196.44 kJ M^?1 and ?219.1 J K^?1 M^?1, 383.56 kJ M^?1, 495.34 kJ M^?1 for 1 and 2, respectively. The sensitivity test results showed that both compounds were sensitive to impact (<5 J) and flame (>20 cm) rather than friction.     

Thermal Behavior and Non-isothermal Decomposition Reaction Kinetics of NEPE Propellant with Ammonium Dinitramide

Thermal decomposition behavior and non‐isothermal decomposition reaction kinetics of nitrate ester plasticized polyether NEPE propellant containing ammonium dinitramide (ADN), which is one of the most important high energetic materials, were investigated by DSC, TG and DTG at 0.1 MPa. The results show that there are four exothermic peaks on DTG curves and four mass loss stages on TG curves at a heating rate of 2.5 K·min^?1 under 0.1 MPa, and nitric ester evaporates and decomposes in the first stage, ADN decomposes in the second stage, nitrocellulose and cyclotrimethylenetrinitramine (RDX) decompose in the third stage, and ammonium perchlorate decomposes in the fourth stage. It was also found that the thermal decomposition processes of the NEPE propellant with ADN mainly have two mass loss stages with an increase in the heating rate, that is the result of the decomposition heats of the first two processes overlap each other and the mass content of ammonium perchlorate is very little which is not displayed in the fourth stage at the heating rate of 5, 10, and 20 K·min^?1 probably. It was to be found that the exothermal peak temperatures increased with an increase in the heating rate. The reaction mechanism was random nucleation and then growth, and the process can be classified as chemical reaction. The kinetic equations of the main exothermal decomposition reaction can be expressed as: dα/dt=10^12.77(3/2)(1?α)[?ln(1?α)]^1/3 e^{?1.723×104/T}. The critical temperatures of the thermal explosion (T_be and T_bp) obtained from the onset temperature (T_e) and the peak temperature (T_p) on the condition of β→0 are 461.41 and 458.02 K, respectively. Activation entropy (ΔS^≠), activation enthalpy (ΔH^≠), and Gibbs free energy (ΔG^≠) of the decomposition reaction are ?7.02 J·mol^?1·K^?1, 126.19 kJ·mol^?1, and 129.31 kJ·mol^?1, respectively.     

A Novel Stable High‐Nitrogen Energetic Compound: Copper(II) 1,2–Diaminopropane Azide

The multi‐ligand coordination compound copper(II) 1,2‐diaminopropane (pn) azide, [Cu(pn)(N₃)₂]_n ( 1 ), was synthesized using pn and azido groups. It was characterized by X‐ray single crystal diffraction, elemental analysis, and FT‐IR spectroscopy. The crystal structure of 1 belongs to the monoclinic system, space group C2/c. The copper(II) cation is six‐coordinated by one pn molecule and four azido ligands with μ‐1 and μ‐1,1,3 coordination modes. Thermogravimetric investigations with a heating rate of 10 K · min^–1 under nitrogen showed one main exothermic stage with a peak temperature of 215.7 °C in the DSC curve. The non‐isothermal kinetics parameters were calculated by Kissinger and Ozawa methods, respectively. The heat of combustion was measured by oxygen bomb calorimetry, and the enthalpy of formation, the critical temperature of thermal explosion, the entropy of activation (ΔS^≠), the enthalpy of activation (ΔH^≠), and the free energy of activation (ΔG^≠) were calculated. The measurements showed that 1 has very high impact, friction, and flame sensitivities.     

Synthesis,spectroscopic, thermal and biological aspects of drug‐based copper(II) complexes

A series of novel complexes of the type Cu(II)(L_n)₂(H₂O)₂]^•xH₂O [where L_n = L _1–4 , these ligands being described as: L ₁ , 2‐({4‐[6,7‐dihydrothieno[3,2‐c]pyridin‐5(4H)‐ylsulfonyl]phenylimino}methyl)phenol, x = 1; L ₂ , 2‐({4‐[6,7‐dihydrothieno[3,2‐c] pyridin‐5(4H)‐ylsulfonyl]phenylimino}methyl)‐5‐(methoxy)phenol, x = 2; L ₃ , 5‐chloro‐2‐({4‐[6,7‐dihydrothieno[3,2‐c]pyridin‐5(4H)‐ylsulfonyl]phenylimino}methyl)phenol, x = 2; and L ₄ , 5‐bromo‐4‐chloro‐2‐({4‐[6,7‐dihydrothieno[3,2‐c]pyridin‐5(4H)‐ylsulfonyl]phenylimino} methyl)phenol, x = 1] was investigated. They were characterized by elemental analysis, IR, ¹H‐NMR, ¹³C‐NMR and electronic spectra, magnetic measurements and thermal studies. The FAB‐mass spectrum of [Cu(II)( L ₁ )₂(H₂O)₂]^•H₂O was determined. A magnetic moment and reflectance spectral study revealed that an octahedral geometry could be assigned to all the prepared complexes. Ligands (L_n) and their metal complexes were screened for their in vitro antibacterial activity against Bacillus subtillis, Pseudomonas aeruginosa, Escherichia coli and Serratia marcescens bacterial strains. Kinetic parameters such as order of reaction (n), the energy of activation (E_a), the pre‐exponential factor (A), the activation entropy (ΔS^≠), the activation enthalpy (ΔH^≠) and the free energy of activation (ΔG^≠) are reported. Copyright © 2011 John Wiley & Sons, Ltd.     

Synthesis and Properties of [Ba(CHZ)(BT)(H2O)2]n as a New Energetic Coordination Compound

In order to enhance the thermal stability of the barium salt of 5,5′‐bistetrazole (H₂BT), carbohydrazide (CHZ) was used to build [Ba(CHZ)(BT)(H₂O)₂]_n as a new energetic coordination compound by using a simple aqueous solution method. It was characterized by FT‐IR spectroscopy, elemental analysis, and single‐crystal X‐ray diffraction. The crystal belongs to the monoclinic P2₁/c space group [a = 8.6827(18) Å, b = 17.945(4) Å, c = 7.2525 Å, β = 94.395(2)°, V = 1126.7(4) ų, and ρ = 2.356 g · cm^–3]. The Ba^II cation is ten‐coordinated with one BT^2–, two shared carbohydrazides, and four shared water molecules. The thermal stabilities were investigated by differential scanning calorimetry (DSC) and thermal gravity analysis (TGA). The dehyration temperature (T_dehydro) is at 187 °C, whereas the decomposition temperature (T_d) is 432 °C. Non‐isothermal reaction kinetics parameters were calculated by Kissinger's method and Ozawa's method to work out E_K = 155.2 kJ · mol^–1, lgA_K = 9.25, and E_O = 158.8 kJ · mol^–1. The values of thermodynamic parameters, the peak temperature (while β → 0) (T_p0 = 674.85 K), the critical temperature of thermal explosion (T_b = 700.5 K), the free energy of activation (ΔG^≠ = 194.6 kJ · mol^–1), the entropy of activation (ΔS^≠ = –66.7 J · mol^–1), and the enthalpy of activation (ΔH^≠ = 149.6 kJ · mol^–1) were obtained. Additionally, the enthalpy of formation was calculated with density functional theory (DFT), obtaining Δ_fH°₂₉₈ ≈ 1962.6 kJ · mol^–1. Finally, the sensitivities toward impact and friction were assessed according to relevant methods. The result indicates the compound as an insensitive energetic material.     

Thermal characterization and kinetic analysis of nano‐ and micro‐Al/NiO thermites: Combined experimental and molecular dynamics simulation study

In the experimental part of this study, thermal properties of the Al and NiO composites in micro‐ and nano‐sized Al are investigated. Differential scanning calorimetry (DSC) analysis of the onset temperatures of ignition, activation energy (E_a), frequency factor (A), rate constant (k), critical ignition temperature of thermal explosion (T_b), and self‐accelerating decomposition temperature (T_SADT), as well as the thermodynamic parameters (ΔS^≠ , ΔH^≠ , and ΔG^≠ ) are used to explore the thermal behavior and analyze the kinetics. Thermal analysis suggests that the mechanism is based on solid–solid diffusion and liquid–gas for the nano‐ and micro‐Al/NiO composite, respectively. Our results indicate that the incorporation of nano‐Al particles can significantly reduce the ignition temperature, E_a, A, k, T_b, and T_SADT. In the second part of this work, molecular dynamics (MD) simulation is used to investigate the behavior of Al/NiO thermite reaction using the Reaxff force field to evaluate the experimental results. Theoretically, MD results show 1,154 K as the reaction ignition temperature, which is in reasonably good agreement with experimental temperature of 893°C (1,166 K). The radial distribution function (RDF) shows that no reaction occurs at 500 K but it is complete at 1,200 K.     

Synthesis, structure analysis and thermodynamics of [Ni(H2O)4(TO)2](NO3)2·2H2O (TO = 1,2,4-triazole-5-one)

A novel complex [Ni(H₂O)₄(TO)₂](NO₃)₂·2H₂O (TO = 1,2,4-triazole-5-one) was synthesized and structurally characterized by X-ray crystal diffraction analysis. The decomposition reaction kinetic of the complex was studied using TG-DTG. A multiple heating rate method was utilized to determine the apparent activation energy (E _a) and pre-exponential constant (A) of the former two decomposition stages, and the values are 109.2 kJ mol^?1, 10^13.80 s^?1; 108.0 kJ mol^?1, 10^23.23 s^?1, respectively. The critical temperature of thermal explosion, the entropy of activation (ΔS ^≠), enthalpy of activation (ΔH ^≠) and the free energy of activation (ΔG ^≠) of the initial two decomposition stages of the complex were also calculated. The standard enthalpy of formation of the new complex was determined as being ?1464.55 ± 1.70 kJ mol^?1 by a rotating-bomb calorimeter.     

Synthesis and Properties of [Cd(HTRTR)2(H2O)4](HTNR)2 as an Energetic Complex

The energetic complex, [Cd(HTRTR)₂(H₂O)₄](HTNR)₂ {HTRTR = 4‐[3‐(1,2,4‐triazol‐yl)‐1,2,4‐triaozle; HTNR^– = styphnic acid anion) was synthesized and characterized by FT‐IR spectroscopy, elemental analysis, and single‐crystal X‐ray diffraction. It crystallizes triclinic in space group P$\bar{1}$ [a = 8.156(2) Å, b = 8.374(2) Å, c = 13.267(4) Å, α = 84.925(11)°, β = 87.016(11)°, γ = 63.683(5)°, V = 808.9(4) ų, ρ = 1.940 g · cm^–3]. The Cd^II ion is six‐coordinate with two HTRTRs and four water molecules. The thermal stabilities were investigated by differential scanning calorimetry (DSC). Non‐isothermal reaction kinetic parameters were calculated by Kissinger's and Ozawa‐Doyle's methods to obtain E_K = 144.0 kJ · mol^–1, lgA_K = 14.22, and E_O = 144.3 kJ · mol^–1. The values of thermodynamic parameters, the peak temperature while β→0 (T_p0), free energy of activation (ΔG^≠), entropy of activation (ΔS^≠), and enthalpy of activation (ΔH^≠) were obtained. Additionally, the enthalpy of formation was calculated by Hess's law on the basis of the experimental constant‐volume heat of combustion measured by bomb calorimetry, obtaining Δ_fH°₂₉₈ = 4985.5 kJ · mol^–1. Finally, the sensitivities toward impact and friction were assessed according to relevant methods. The result indicates it as an insensitive energetic material.     

钐(Ⅲ)与不对称希夫碱配合物的合成、表征和热分解反应动力学

A new unsymmetrical Schiff base zwitterion （Ⅲ） was synthesized using L-lysine, salicylaldehyde and 2-hydroxy-l-naphthaldehyde. Samarium（Ⅲ） complex of this ligand [SmL（NO3）]NO3·2H2O has been prepared and characterized by elemental analyses, IR, UV and molar conductance. The thermal decomposition kinetics of the complex for the second stage was studied under non-isothermal condition by TG and DTG methods. The kinetic equation may be expressed as dα/dt=3/2Ae^E/RT（1-α）^2/3[1-（1 -α）^1/3）]^-1. The kinetic parameters （E, A）, activation entropy △S^x and activation free-energy △G^x were also gained.     

Thermal behaviour of dimethylgold(III) carboxylates

The thermal properties of dimethylgold(III) carboxylates of general formula [(CH₃)₂Au(OOCR)]₂ (R=methyl (1), tert-buthyl (2), trifluoromethyl (3), or phenyl (4)) in solid state have been investigated by the thermogravimetric analysis. The temperature dependences of saturated vapour pressure of complexes have been studied by the Knudsen effusion method with mass spectrometric indication. The thermodynamic parameters Δ_sub H _T ⁰ and Δ_sub S _T ⁰ of the sublimation processes have been calculated. Thermal decomposition of the vapour of complexes 1 and 2 has been studied by means of high temperature mass spectrometry in vacuum, and by-products of decomposition have been determined.     

Excess properties and spectroscopic studies of binary system 1,4-butanediol + water at T = (293.15, 298.15, 303.15, 308.15, 313.15 and 318.15) K

Density and dynamic viscosity data were measured over the whole concentration range for the binary system 1,4-butanediol (1) + water (2) at T = (293.15, 298.15, 303.15, 308.15, 313.15, and 318.15) K as a function of composition under atmospheric pressure. Based on density and dynamic viscosity data, excess molar density (ρ^E), dynamic viscosity deviation (Δν) and excess molar volume (V_m^E) were calculated. From the dynamic viscosity data, excess Gibbs energies (ΔG*^E), Gibbs free energy of activation of viscous flow (ΔG*), enthalpy of activation for viscous flow (ΔH*) and entropy of activation for viscous flow (ΔS*) were also calculated. The ρ^E, V_m^E, Δν and ΔG*^E values were correlated by a Redlich?Kister-type function to obtain the coefficients and to estimate the standard deviations between the experimental and calculated quantities. Based on FTIR and UV spectral results, the intermolecular interaction of 1,4-butanediol with H₂O was discussed.     

鬼臼毒素及其衍生物热分解反应的动力学研究

The thermal behavior and thermal decomposition kinetic parameters of podophyllotoxin （1） and 4 derivatives, picropodophyllin （2）, deoxypodophyllotoxin （3）, fl-apopicropodophyllin （4）, podophyllotoxone （5） in a temperature-programmed mode have been investigated by means of DSC and TG-DTG. The kinetic model functions in differential and integral forms of the thermal decomposition reactions mentioned above for first stage were established. The kinetic parameters of the apparent activation energy Ea and per-exponential factor A were obtained from analy- sis of the TG-DTG curves by integral and differential methods. The most probable kinetic model function of the decomposition reaction in differential form was （1- a）^2 for compounds 1-3,2/3·a^-1/2 for compound 4 and 1/2（1-a）·[-In（1-a）]^-1 for compound 5. The values of Ea indicated that the reactivity of compounds 1-5was increased in the order： 5〈4〈2〈1〈3. The values of the entropy of activation △S^≠, enthalpy of activation △H^≠ and free energy of activation △G^≠ of the reactions were estimated. The values of △G^≠ indicated that the thermal stability of compounds 1-3 with the samef（a） was increased in the order： 2〈3〈1.     

A feature on ensuring safety of superfine explosives

To probe the dependence of particle size on the safety of nitroamine explosives, coarse RDX and HMX were comminuted to nanometer particles by an improved superfine mill. Their thermolysis characteristics were studied by thermal analysis and described via calculating some thermodynamic and kinetic parameters such as the activation free-energy (ΔG ^≠), activation enthalpy (ΔH ^≠), activation entropy (ΔS ^≠), apparent activation energy (E), critical temperature of thermal explosion (T _b), and critical heating rate of thermal explosion ( $ ({\text{d}}T/{\text{d}}t)_{{T_{\text{b}} }} $ ). After comminuted, the values of T _b and $ ({\text{d}}T/{\text{d}}t)_{{T_{\text{b}} }} $ were increased. However, the values of ΔH ^≠, ΔS ^≠, ΔG ^≠, and E for nanoexplosives were close to those of microexplosives, which mean decreasing particle size into nanometer did not distinctly influence the thermolysis characteristic of nitroamines. The safety of the nanoexplosives was practically assessed by testing their impact, friction, and shock sensitivities. Results indicated that nano nitroamines presented obviously higher safety than the micro-counterparts. Especially in Small Scale Gap Test, the shock sensitivity of nano-RDX and nano-HMX decreased by about 45 and 56% compared with that of micro-RDX and micro-HMX, respectively.     

Novel drug‐based Fe(III) heterochelates: synthetic,spectroscopic, thermal and in‐vitro antibacterial significance

A series of novel heterochelates of the type [Fe(Aⁿ)(L)(H₂O)₂]^?mH₂O [where H₂Aⁿ = 4,4′‐(arylmethylene)bis(3‐methyl‐1‐phenyl‐4,5‐dihydro‐1H‐pyrazol‐5‐ol); aryl = 4‐nitrophenyl, m = 1 (H₂A¹); 4‐chlorophenyl, m = 2 (H₂A²); phenyl, m = 2 (H₂A³); 4‐hydroxyphenyl, m = 2 (H₂A⁴); 4‐methoxyphenyl, m = 2 (H₂A⁵); 4‐hydroxy‐3‐methoxyphenyl, m = 1.5 (H₂A⁶); 2‐nitrophenyl, m = 1.5 (H₂A⁷); 3‐nitrophenyl, m = 0.5 (H₂A⁸); p‐tolyl, m = 1 (H₂A⁹) and HL = 1‐cyclopropyl‐6‐fluoro‐4‐oxo‐7‐(piperazin‐1‐yl)‐1,4‐dihydroquinoline‐3‐carboxylic acid] were investigated. They were characterized by elemental analysis (FT‐IR, ¹H‐ & ¹³C‐NMR, and electronic) spectra, magnetic measurements and thermal studies. The FAB‐mass spectrum of [Fe(A³)(L)(H₂O)₂]^?2H₂O was determined. Magnetic moment and reflectance spectral studies revealed that an octahedral geometry could be assigned to all the prepared heterochelates. Ligands (H₂Aⁿ) and their heterochelates were screened for their in‐vitro antibacterial activity against Bacillus subtilis, Staphylococcus aureus, Escherichia coli and Serratia marcescens bacterial strains. The kinetic parameters such as order of reaction (n), the energy of activation (E_a), the pre‐exponential factor (A), the activation entropy (ΔS^#), the activation enthalpy (ΔH^#) and the free energy of activation (ΔG^#) are reported. Copyright © 2009 John Wiley & Sons, Ltd.