Synergistic Catalytic Effect of a Series of Energetic Coordination Compounds based on Tetrazole‐1‐acetic Acid on Thermal Decomposition of HMX

A series of energetic coordination compounds [Co(tza)₂}_n ( 1 ), [Bi(tza)₃]_n ( 2 ), {[Cu₄(tza)₆(OH)₂] · 4H₂O}_n ( 3 ), [Mn(tza)₂]_n ( 4 ), {[Bi(tza)(C₂O₄)(H₂O)] · H₂O}_n ( 5 ) and [Fe₃O(tza)₆(H₂O)₃]NO₃ ( 6 ) based on tetrazole‐1‐acetic acid (Htza) were synthesized though environmentally friendly methods. The coordination compounds were characterized by elemental analyses, IR spectroscopy, single‐crystal and powder X‐ray diffraction (PXRD), thermogravimetric analyses (TG), and differential scanning calorimetry (DSC). Their catalytic performances and the synergetic catalytic effects between 1 and 2 , 3 and 4 , 5 and 6 on the thermal decomposition of octahydro‐1,3,5,7‐tetranitro‐1,3,5,7‐tetrazocine (HMX) were all investigated by DSC. The results revealed that compounds 1 – 6 are thermally stable energetic compounds and they all exhibit high catalytic action for HMX thermal decomposition. The catalytic effects of the compounds on HMX thermal decomposition are closely related to the oxides, which come from the decomposition of the compounds, but have no positive relationships with the heat releases of the compounds themselves. Moreover, the synergetic catalytic effects between 1 and 2 , 3 and 4 , 5 and 6 were observed. Their mixtures at different mass ratio have different synergetic catalytic effects, and the sequence of the biggest synergetic index (SI) in each system is copper‐manganese system (compounds 3 and 4 ) > iron‐bismuth system (compounds 5 and 6 ) > cobalt‐bismuth system (compounds 1 and 2 ), indicating that the synergistic catalytic effects are mainly related to the combination and the proportion of the compounds.     

The Synthesis,Spectral, and Electrochemical Characterization of Novel Alkoxybenzoquinone Derivatives

The novel monosubstituted benzoquinone compounds 3e , 3g , 3h ; 2,5‐O‐ substituted benzoquinone compounds 4a , 4b , 4c , 4d , 4e 4g and known compound 4h and 2,6‐O‐ substituted benzoquinone compounds 5e , 5f , 5g , 5h were obtained by the reaction of p‐chloranil ( 1 ) and related alcohol compounds in potassium carbonate (K₂CO₃) solution of acetonitrile or chloroform with Et₃N. The novel cyclic compounds 7 , 8 and 10 , 11 were obtained from the reaction of p‐chloranil ( 1 ) and diols in potassium carbonate (K₂CO₃) solution of acetonitrile at room temperature. The structures of novel compounds were characterized by using micro analysis, FT‐IR, ¹H‐NMR, ¹³C‐NMR, MS and cyclic voltammetry.     

Classification of structurally related compounds fromAstragalus extract by correlation of the logk w andS

Summary The linear relationship between logk _w andS derived from molecular interactions and statistical thermodynamics was investigated by four series of different polar probe solutes. For each series of similar polar solutes, structurally related compounds with similar dipolarity/polarizability and hydrogen bonding energy, a linear relationship between logk _w andS was obtained. The more similar the solutes, the greater were the regression coefficients obtained. For two series of solutes with different strong polar groups resulting in different dipolarity/polarizability and hydrogen bonding energy, two parallel lines were observed in the logk _w-S plots. Each line represented one series of compounds and the distance between them indicated the difference in the dipolarity/polarizability and hydrogen bonding energy. Based on the parallel lines implying information on structurally related compounds in the logk _w-S plot, a method of classification of structurally related compounds was put forward and the linear logk _w-S correlation for unknown components in nonaqueous RP-HPLC analysis ofAstragalus extract with isopropanol-methanol mobile phase was studied. Two nearly parallel lines were obtained in the logk _w-S plot and two series of structurally related compounds were classified in this way.     

Cationic radius ratio and formation of K2NiF4-type compounds

A survey of known compounds which can assume K₂NiF₄-type structure at least over a certain P, T range was made. The cationic radius ratios r_A/r_B of this family of compounds were found to vary over a relatively narrow range of values around 2.00, in contrast to the much wider ranges known for other important A₂BX₄ structure groups, e.g., β-K₂SO₄, thenardite, olivine, etc., providing thereby a constraint on the crystal chemical variabilities in this group of compounds. Usefulness of the simple size parameter r_A(IX)/r_B(VI) in predicting formation of new K₂NiF₄-type compounds is discussed.     

Determination of the n‐octanol/water partition coefficients of weakly ionizable basic compounds by reversed‐phase high‐performance liquid chromatography with neutral model compounds

A strategy to utilize neutral model compounds for lipophilicity measurement of ionizable basic compounds by reversed‐phase high‐performance liquid chromatography is proposed in this paper. The applicability of the novel protocol was justified by theoretical derivation. Meanwhile, the linear relationships between logarithm of apparent n‐octanol/water partition coefficients (logK_ow′′) and logarithm of retention factors corresponding to the 100% aqueous fraction of mobile phase (logk_w) were established for a basic training set, a neutral training set and a mixed training set of these two. As proved in theory, the good linearity and external validation results indicated that the logK_ow′′–logk_w relationships obtained from a neutral model training set were always reliable regardless of mobile phase pH. Afterwards, the above relationships were adopted to determine the logK_ow of harmaline, a weakly dissociable alkaloid. As far as we know, this is the first report on experimental logK_ow data for harmaline (logK_ow = 2.28 ± 0.08). Introducing neutral compounds into a basic model training set or using neutral model compounds alone is recommended to measure the lipophilicity of weakly ionizable basic compounds especially those with high hydrophobicity for the advantages of more suitable model compound choices and convenient mobile phase pH control.     

X-ray,SEM, and DSC studies of ferroelectric Pb<Subscript>1−<Emphasis Type="Italic">X</Emphasis></Subscript>Ba<Subscript><Emphasis Type="Italic">X</Emphasis></Subscript>TiO<Subscript>3</Subscript> ceramics

The polycrystalline ferroelectric compounds of general formula Pb_1−X Ba _X TiO₃ with X = 0.00, 0.1, 0.2 and 0.5 were prepared by high temperature solid-state reaction technique using high purity oxides and carbonates. The compounds formation was confirmed by X-ray diffraction and all the X-ray peaks were indexed with tetragonal structure of space group P4mm. Morphology and particle size of the compounds were obtained using scanning electron microscopy. Ferroelectric phase transition, enthalpy change, and specific heat of the compounds were obtained using modulated differential scanning calorimetry. It was observed that the phase transition temperature decreased linearly with the increase of substitution concentration.     

Synthesis,characterization and antibacterial studies of some new tellurated azo compounds

A series of tellurated azo compounds [i.e. (4-HOC₆H₄N=N-Ar)TeBr₃ and (4-HOC₆H₄N=N-Ar)₂TeBr₂, where Ar=5-BrC₆H₃, 5-CH₃C₆H₃ and 5-NO₂C₆H₃] were prepared by the reaction of the corresponding 2-(4-hydroxyphenylazo)aryl mercury chloride with tellurium tetrabromide in 1:1 and 2:1?mole ratio, respectively in dry dioxane as a solvent. The reduction of (4-HOC₆H₄N=N-Ar)TeBr₃ by hydrazine hydrate gave the corresponding ditelluride (i.e., (4-HOC₆H₄N=N-Ar)₂Te₂). Treatment of (4-HOC₆H₄N=N-Ar)₂TeBr₂ with hydrazine hydrate afforded the corresponding tellurides, (4-HOC₆H₄N=N-Ar)₂Te), in good yields. The structures of all newly synthesized compounds were assigned on the basis of their elemental and spectroscopic data. The antibacterial activity of tellurated azo compounds along with mercurated azo compounds was tested with agar diffusion method against the bacteria strains Staphylococcus aureus and Escherichia coli. The antibacterial activities of tellurated azo compounds were in some cases equal or better than those of the reference drug. The mercurated azo compounds were found to be the more antibacterial activity of than those of tellurated azo compounds.     

Synthesis,structural and larvicidal studies of a series of triorganotin chrysanthemumates

A series of triorganotin chrysanthemumates (2,2‐dimethyl‐3‐(2‐methyl‐1‐propenyl)cyclopropanecarboxylates) (R₃SnO₂CC₉H₁₅) where R = methyl, ethyl, n‐butyl and phenyl was synthesized. The solid state structures were deduced using infrared (IR) and Mössbauer spectroscopies. The spectroscopic results indicated that all the compounds were found to be five‐coordinated in the solid state. Based on the NMR results, all the compounds are tetrahedral in solution. Larvicidal activities of the compounds were evaluated against the second instar stage of Aedes aegypti, Anopheles stephensi and Culex pipiens quinquefasciatus mosquitoes. The toxicity results indicated that these compounds of triorganotins were effective larvicides against all three species of larvae. Copyright © 2011 John Wiley & Sons, Ltd.     

哒嗪酮类α1-肾上腺素受体拮抗剂的合成和生物活性研究

将苯(氧)乙胺和苯氧烷胺类α₁-肾上腺素受体拮抗剂中的苯(氧)乙胺、苯氧烷胺片段引入哒嗪酮类化合物中, 设计、合成了30个新的含哒嗪酮环的α₁-肾上腺素受体拮抗剂. 所有新化合物的结构均经¹H NMR, IR, HRMS确证. 生物活性测试表明28个目标物对α₁-肾上腺素受体有较好的拮抗作用(pA₂＞6.00), 化合物6o, 6p, 6q, 6v, 6x, 6y, 10c, 10d的pA₂值＞7.00.     

Cage Compounds of Phosphorus and the Heavier Group 14 Elements

The Sn/P cage compounds [Sn₁₀(tBuP)₄] ( 1 ) and [Sn₁₀(tBuP)₇Cl₄] ( 2 ) were obtained by the reaction of LitBuPH with SnBr₂ and SnCl₂, respectively. Theoretical calculations confirm that the tin atoms in 2 feature different formal oxidation states. The reaction of PbCl₂ with LitBuPH and LiPHSiiPr₃ yields the Pb/P cage compounds [Pb₇(tBuP)₇] ( 3 ) and [Pb₆(PSiiPr₃)₆] ( 4 ), respectively, that represent new derivatives of known polyhedrons of this class of compounds. The new products were characterized by X‐ray diffraction, elemental analysis and partially by MS and MAS‐NMR spectroscopy.     

Synthesis and optical behaviors of 2-(9-phenanthrenyl)-, 2-(9-anthryl)-, and 2-(1-pyrenyl)-1-alkylimidazole homologues

Eight 2-(9-phenanthrenyl)-, 2-(9-anthryl)- and 2-(1-pyrenyl)-1-alkyl-benzimidazole compounds, three 2-(9-anthryl)-1-alkylphenanthroimidazole compounds and five 4,5-diphenyl-1-alkyl-2-(9-anthryl)imidazole compounds were synthesized by alkylation reactions of the corresponding benzimidazole, phenanthroimidazole or imidazole compounds. 2-(10-Bromo-9-anthryl)-1-alkyl-benzimidazole compounds were prepared by bromination reaction of 2-(9-anthryl)-1-alkylbenzimidazole compounds. All the synthesized compounds were characterized by elemental analysis, ¹H NMR, ¹³C NMR, MS or HRMS; their absorption coefficients (), maximum absorption λ_amax, fluorescence emission maximum λ_em, Stokes shifts and fluorescence quantum yields (Φ_F) in ethyl acetate were determined; their fluorescent lifetimes (T₁ and T₂) were measured in ethyl acetate and in solid state, respectively. The crystal structure of 2-(9-anthryl)-1-n-butyl-4,5-diphenylimidazole (12a) was determined to be triclinic, space group P-1 types, using single crystal X-ray crystallography technique. The results showed that these compounds exhibited moderate fluorescence-emission abilities and higher solubility in most organic solvents than their corresponding starting materials. The relationships between the optical behaviors and structures for these compounds were discussed.     

Preparation and Characterization of the Nanocomposites SiO2/H-Bond Hydrogensulphate (Hydrogenselenate)

The nanocomposites representing interesting H-bond compounds (Na₃H(SO₄)₂, RbHSO₄, RbHSeO₄, and Rb₃H(SeO₄)₂) in the silica matrix were prepared by the sol-gel method. Resulting samples were characterised by X-ray diffraction, IR spectroscopy and electron microscopy. Transition temperatures of the nanocomposites were determined using DSC and compared with the T _C of the pure bulk active compounds. The shifts of the T _C towards lower temperatures or the disappearing of the certain effects in the case nanocomposites were observed. A possible explanation of these phenomena was proposed using the analogy with the superparamagnetic compounds.     

pH‐Directed Synthesis of Two Luminescent Zinc(II) Coordination Compounds based on 5‐Aminotetrazole‐1‐propanoic Acid

Two Zn^II‐tetrazole‐carboxylate coordination compounds are reported, mononuclear [Zn(atzpa)₂(H₂O)₄] · 2H₂O ( 1 ) and one‐dimensional [Zn(atzpa)₂(H₂O)₂]_n ( 2 ), derived from 5‐aminotetrazole‐1‐propanoic acid (Hatzpa). The structures of both compounds are determined by the pH value of the reaction system. The luminescence properties of Hatzpa and the compounds were investigated at room temperature in the solid state. Furthermore, differential scanning calorimetry (DSC) and thermogravimetric‐differential thermogravimetric (TG‐DTG) analyses were applied to evaluate the thermal decomposition behavior of such compounds. The relevant thermodynamic parameters (ΔH, ΔS, and ΔG) of the decompostion process of compound 1 were calculated, as well.     

Magnetic and Crystallographic Properties of LnCrO4 (Ln=Nd, Sm, and Dy)

Zircon-type compounds LnCrO₄ (Ln=Nd, Sm, and Dy) were prepared. Their precise crystal structures at room temperature were determined from X-ray diffraction measurements. These compounds have a tetragonal system with space group I4₁/amd. Magnetic susceptibility and specific heat measurements have been performed for all the compounds in the temperature range between 1.8 and 300 K. For NdCrO₄, an antiferromagnetic transition was found at 25.2 K. SmCrO₄ and DyCrO₄ show magnetic transitions at 15.0 and 22.8 K, respectively. In addition, structural phase transitions were observed at 58.5 and 31.2 K, respectively. For DyCrO₄, the crystal structure below the transition temperature was determined by low-temperature powder X-ray diffraction measurements to be orthorhombic with space group Imma.     

两种希夫碱对大肠杆菌抗菌活性的微量热法研究

The microcalorimetric method was used to study the antibacterial activity of two newly synthesized Schiff base compounds （H2L3＇ and H2L3） on Escherichia coli, trying to obtain the action on both of multiplying bacteria and non-multiplying bacteria at one experiment. The metabolic power-time curves of the bacteria treated with the compounds were obtained, and the thermokinetic parameters were analyzed, from which the antibacterial activities of these compounds were evaluated. The results showed that both of the two compounds have good activity on aerobic multiplying metabolism of E. coli, with the value of ICso 75.8 and 168.8 mg/L respectively, but have not effective action on fermentation metabolism of E. coli. The action of the compounds on the non-multiplying metabolism was investigated by taking the heat output of E. coli in the stationary phase as the guideline of the activity. The value of MSCso （minimum stationary-cidal concentration 50） of them is 118 and 187.5 mg/L, respectively. So, H2L^3 has stronger antibacterial action on E. coli than H2L^3 either for multiplying bacteria or non-multiplying bacteria, and their activity on the aerobic multiplying bacteria of E. coil is mainly shown. It does strongly suggest that the calorimetric method should play an important role in the fight against the drug-resistant bacteria.     

Effects of cis/trans-Configuration and Ligand Substitution of the Cyanidometal Bridge on Metal to Metal Charge Transfer Properties in Mixed Valence Complexes

To investigate the effects of cis/trans-configuration of the cyanidometal bridge and the electron donating ability of the auxiliary ligand on the cyanidometal bridge on metal to metal charge transfer (MMCT) in cyanidometal-bridged mixed valence compounds, two groups of trinuclear cyanidometal-bridged compounds cis/trans-[Cp(dppe)Fe(μ-NC)Ru(4,4’-dmbpy)₂(μ-CN)Fe(dppe)Cp][PF₆]_n (n=2 ( cis/trans - 1[PF₆]₂ ), 3 ( cis/trans - 1[PF₆]₃ ), 4 ( cis/trans - 1[PF₆]₄ )) and cis/trans-[Cp(dppe)Fe(μ-NC)Ru(bpy)₂(μ-CN)Fe(dppe)Cp][PF₆]₃ ( cis/trans - 2[PF₆]₃ ) were synthesized and fully characterized. The experimental results indicate that for these one- and two-electron oxidation mixed valence compounds, the trans-configuration compounds are more beneficial for MMCT than the cis-configuration compounds, and increasing the electron donating ability of the auxiliary ligand on the cyanidometal bridge is also conductive to MMCT. Moreover, compounds cis/trans - 1[PF₆]_n (n=3, 4) and cis/trans - 2[PF₆]₃ belong to localized compounds by analyzing the experimental characterization results, supported by the TDDFT calculations.     

Synthesis,structure and in vitro cytotoxicity testing of some 2‐aroylbenzofuran‐3‐ols

Five 2‐aroyl‐5‐bromobenzo[b]furan‐3‐ol compounds (two of which are new) and four new 2‐aroyl‐5‐iodobenzo[b]furan‐3‐ol compounds were synthesized starting from salicylic acid. The compounds were characterized by mass spectrometry and ¹H NMR and ¹³C NMR spectroscopy. Single‐crystal X‐ray diffraction studies of four compounds, namely, (5‐bromo‐3‐hydroxybenzofuran‐2‐yl)(4‐fluorophenyl)methanone, C₁₅H₈BrFO₃, (5‐bromo‐3‐hydroxybenzofuran‐2‐yl)(4‐chlorophenyl)methanone, C₁₅H₈BrClO₃, (5‐bromo‐3‐hydroxybenzofuran‐2‐yl)(4‐bromophenyl)methanone, C₁₅H₈Br₂O₃, and (4‐bromophenyl)(3‐hydroxy‐5‐iodobenzofuran‐2‐yl)methanone, C₁₅H₈BrIO₃, were also carried out. The compounds were tested for their in vitro cytotoxicity on the four human cancer cell lines KB, Hep‐G2, Lu‐1 and MCF7. Six compounds show good inhibiting abilities on Hep‐G2 cells, with IC₅₀ values of 1.39–8.03 µM.     

The coupled TG-MS investigations of lanthanide(III) nitrate complexes with hexamethylenetetramine

New transition metal compounds of the general formula Ln(NO₃)₃·2[N₄(CH₂)₆]·nH₂O, where Ln = La, Nd, Sm, Gd, Tb, Dy, Er, Lu, and n = 7-12, were obtained. The compounds and the gases evolved in the course of their thermal decomposition were characterised by thermogravimetric analysis. The measurements were carried out in air and argon environment in order to compare the intermediate products, final products and the mechanism of the thermal decomposition. The combined TG-MS system was used to identify the main volatile products of thermal decomposition and fragmentation processes of the obtained compounds. This revised version was published online in July 2006 with corrections to the Cover Date.     

含二齿膦配体的二羰基铁化合物的制备及光诱导释放一氧化碳性能

一氧化碳释放剂(CORM)为CO在人体的精准输送提供了便利。为提高CORM的稳定性,以[Fe(CO)₄I₂]为前驱体,通过与二齿膦配体dppe、dppp、PNP(dppe=1,2-双(二苯基膦酰)乙烷,dppp=1,3-双(二苯基膦酰)丙烷,PNP=N-环己基-N-(二苯基膦酰)-1,1-二苯基膦胺(Ph₂PN(cyclohexyl)PPh₂)的配位取代反应制得了二齿膦二羰基铁化合物1~3,并利用FT-IR、UV-Vis、NMR、元素分析、单晶X射线衍射(化合物2、3)进行表征。通过红外光谱法研究了化合物1~3的降解释放CO性能,以评估其作为CORM的潜能。在二甲亚砜溶剂中、黑暗条件下这些化合物表现出良好稳定性;但在可见光(红光、绿光、蓝光)照射下,均可降解释放CO,其降解速率与光源的能量和化合物的结构有关。此外,在蓝光和绿光照射下,发现化合物1和2可从顺式构型向反式构型发生转化,而红光下因能量不足未见构型转化。     

Determination of Octanol–Water Partition Coefficients,Water Solubility and Vapour Pressures of Alkyl-lead Compounds

Physico-chemical properties of alkyl-lead compounds, namely aqueous solubility, octanol–water partition coefficient ( K _ow), vapour pressure and Henry's Law constant, have been determined. Vapour pressures of trialkyl-lead salts at different temperatures were measured by a gas-saturation technique in which air was passed slowly through a glass column packed with pure solid alkyl-lead compounds. K _ow of tetra-alkyl-lead (TAL) and trialkyl-lead (TriAL) were determined under different salinity and pH conditions, and the latter were related to the species (R₃Pb⁺, R₃PbOH⁰ or R₃PbCl⁰) dominating under a particular set of conditions. Regression calculations incorporating melting point corrections relate water solubility to K _ow, and provide a means of estimating either parameter for a wider range of compounds.