2,3-二氰基-2,3-二(p-X苯基)丁二酸二乙酯的分子构型和取代基电子效应对13C NMR谱的影响

测定了meso-和dl-2,3-二氰基-2,3-二(p-X苯基)丁二酸二乙酯(X=OCH₃,CH₃,H,Cl,NO₂)的¹³CNMR谱。结果表明,中心碳-碳键两端相连基团的各碳原子的化学位移值相同,与dl-异构体相比,所有相应meso-异构体的乙氧羰基¹³CNMR吸收峰均处于高场。苯环对位取代基的Hammett基团常数σ与氰基碳原子和乙氧羰基中的羰基碳及次甲基碳的化学位移间线性相关,而且meso-异构体比dl-异构体有更好的线性关系。     

2,3-二氰基-2,3-二(p-取代苯基)丁二酸二乙酯的合成及其在苯乙烯中的分解

合成了2,3-二氰基-2,3-二(p-X苯基)丁二酸二乙酯(X=OCH₃,CH₃,Cl,NO₂),分离出它们的meso和dl异构体。经元素分析、¹HNMR、IR、MS和X射线晶体结构分析确定了各异构体的结构和构型。在100℃测定了各异构体在苯乙烯中的分解速率常数k_d,结果表明,除X=OCH₃外,meso异构体的k_d均比dl异构体的大,除X=NO₂外,苯环对位取代基对k_d的影响顺序为OCH₃>CH₃>Cl>H,     

紫杉醇在二甲基亚砜中的溶解行为

用微热量热仪测量紫杉醇在二甲亚砜中的溶解焓。 得到了微分溶解热（Δ_difH_m）和积分溶解热（Δ_solH_m）,建立了热量与溶质的量之间的关系式。 并得到了紫杉醇在二甲亚砜中溶解过程的动力学方程：da/dt=2.92×10^-4×(1-a)^1.00,半衰期t_1/2=50.43 min,Δ_solH_m=32.67 kJ/mol以及Δ_solS_m=-204.93 J/(mol·K)。结果表明,利用微热量热法可以为药物半衰期的测定提供一种简便的方法,并可为紫杉醇的临床应用提供理论参考。     

meso和dl 2,3-二氰基-2,3-二(p-取代苯基)丁二酸二乙酯的~1H NMR研究

测定了meso和dl 2,3-二氰基-2,3-二(p-X苯基)丁二酸二乙酯(X=OCH_3,CH_3,H,Cl,NO_2)的~1H NMR谱及X为CH_3相应二乙酯的~1H Noesy谱。在meso和dl异构体中,苯环m-~1H的化学位移与p-X的Hammett基团常数σ呈线性关系,c~1H的化学位移仅受分子构型的影响,;△δdl-meso为负值,乙氧基中CH_2和CH_3的质子化学位移也只受分子构型的影响,△δdl-meso均为正值。     

多氟代、多氯代和多溴代二苯并对二噁英化合物的一些性质的比较研究

采用密度泛函理论(DFT)方法, 在B3LYP/6-311G**和B3LYP/6-31G*两种水平上, 对76种多氟代二苯并对二噁英系列化合物(PFDDs)进行了几何构型的全优化, 并计算了各分子在298.15 K, 1.013×10⁵ Pa的标准状态下的热力学参数. 基组从6-31G*增大到6-311G**没有显著改变标准生成热(Δ_fH^?)、标准生成自由能(Δ_fG^?)和标准熵(S^?)数值. 根据B3LYP/6-311G**水平计算得到的Δ_fG^?的相对大小, 求得PFDDs同数目取代氟原子的各异构体的相对稳定性的顺序. 采用基团贡献法计算了多溴代二苯并对二噁英(PBDDs)、多氯代二苯并对二噁英(PCDDs)和PFDDs的辛醇-水分配系数(lg K_ow). 并将PFDDs的Δ_fH^?, Δ_fG^?, S^?和lg K_ow的计算结果与PBDDs和PCDDs的相关数值进行了比较. 同时, 计算了PFDDs各组异构体化合物的生成反应相对速率常数, 采用统计热力学程序计算了这些化合物在200至1800 K的恒压摩尔热容(C_p,m), 并用最小二乘法求得C_p,m与温度之间的相关方程, 发现C_p,m与T, T^－1和T^－2之间有着很好的相关性.     

无水苯甲酸锂的合成、结构表征及热化学研究

用分析纯苯甲酸和一水氢氧化锂作为反应物, 采用水热合成法制得苯甲酸锂. 利用X射线粉末衍射、FTIR、元素分析及化学分析等方法对样品进行组成和结构表征. 采用精密自动绝热热量计测量了其在80~400 K范围内的摩尔热容, 利用最小二乘法将此温区热容实验值对折合温度进行拟合, 得到热容随温度变化的多项式方程. 通过设计合理的热化学循环, 选用0.1 mol/L HCl溶液作为量热溶剂, 利用等温环境溶解-反应热量计分别测定合成反应的反应物和产物在所选溶剂中的溶解焓, 得到反应焓Δ_rH_m⁰=-(9.75±0.27) kJ/mol. 利用Hess定律计算出苯甲酸锂的标准摩尔生成焓Δ_fH_m⁰(C₆H₅COOLi, s)=-(307.82±0.57) kJ/mol.     

8-或6-(3-氯苯甲酰)香豆素衍生物的合成、表征、生物活性及与牛血清白蛋白的相互作用

合成了2个新化合物7-羟基-8-(3-氯苯甲酰基)-4-甲基香豆素(1)和7-羟基-6-(3-氯苯甲酰基)-4-甲基香豆素(2). X射线单晶衍射分析表明, 2个化合物的晶体同属于单斜晶系, P2₁/c空间群, 化合物1: a=1.21527(14) nm, b=1.01550(12) nm, c=1.5045(2) nm, β=112.377(2)°, V=1.7169(4) nm³, D_c=1.396 g/cm³, Z=4, F(000)=752, R₁=0.0415, wR₂=0.0981[I>2σ(I)], S=1.063; 化合物2: a=2.0168(2) nm, b=0.76229(12) nm, c=2.25497(17) nm, β=123.987(6)° , V=0.8745(6) nm³, D_c=1.454 g/cm³, Z=8, F(000)=1296, R₁=0.0604, wR₂=0.1384[I>2σ(I)], S=0.948. 抗菌实验结果表明, 2个化合物对大肠杆菌(E. coli)、 枯草杆菌(B. subtilis)和金色葡萄球菌(S. aureus) 均有中等程度的抑制作用; 体外抗氧化实验结果表明, 2个化合物对超氧阴离子自由基(O₂^-·)、 羟基自由基(·OH)和二苯代苦味肼基自由基(DPPH·)均有良好的清除能力. 采用荧光光谱法研究了不同温度下2个化合物与牛血清白蛋白(BSA)的相互作用, 结果表明, 2个化合物对BSA 的荧光猝灭均属于静态猝灭; 热力学数据表明, 化合物1(ΔH>0, ΔS>0, ΔG<0)与BSA主要以疏水作用力相结合, 化合物2(ΔH<0, ΔS<0, ΔG<0)与BSA主要以氢键或范德华力相结合; BSA与化合物1和化合物2间的距离分别为2.59和2.38 nm, 说明2个化合物与BSA 之间可能发生了非辐射能量转移.     

meso-5,10,15,20-四[4-(N-吡咯烷基)苯基]卟啉的合成及对牛血清白蛋白的作用

基于卟啉对癌细胞的特殊亲和作用和吡咯烷化合物的抗肿瘤及抗癌活性,设计并合成了具有吡咯烷结构的新型卟啉化合物--meso-5,10,15,20-四[4-(N-吡咯烷基)苯基]卟啉(TBPPH₂),利用荧光光度法和紫外-可见分光光度法研究了TBPPH₂与牛血清白蛋白(BSA)的相互作用.实验发现,TBPPH₂利用疏水作用力进入BSA的疏水性腔,与BSA形成配合物并引起BSA的静态荧光猝灭.在TBPPH₂与BSA的相互作用过程中,TBPPH₂与BSA以摩尔比1∶1牢固结合,TBPPH₂与BSA分子中色氨酸间的最近距离r=2.4nm.反应平衡常数K_A=2.51×10⁴L/mol,反应熵变ΔS=84.18J/(mol·K),TBPPH₂与BSA的结合常数K_B=5.13×10⁵L/mol.研究结果表明,吡咯烷基卟啉可能成为一类新型的抗肿瘤及抗病毒药物.     

娃儿藤碱类似物DCB-3501的全合成及其细胞毒性

以3,4-二甲氧基苯甲醛与3,4-二甲氧基苯乙酸为起始原料,经Perkin缩合、自由基氧化偶联反应、Swern氧化、还原胺化及付克酰基化等7步反应全合成了娃儿藤碱类似物DCB-3501,其结构经¹H NMR和ESI-MS确证。体外细胞毒性测试结果表明：DCB-3501对人结肠癌细胞HCT116、人胃癌细胞BGC-823、人肝癌细胞HepG-2、人宫颈癌细胞HeLa和人大细胞肺癌细胞H460的IC₅₀分别为20.0 μmol·L^-1, 50.9 μmol·L^-1, 2.1 μmol·L^-1, 65.8 μmol·L^-1和30.8 μmol·L^-1。     

新型氯化三苯基锡(1,4-二氢-2,3-二苯基四氮唑酮)配合物的合成及其性能

以三苯基氯化锡和二苯碳酰二肼为原料,在乙醇-钠中反应合成了一个新型的氯化三苯基锡(1,4-二氢-2,3-二苯基四氮唑酮)配合物（1）,其结构经FT-IR,元素分析和X-射线单晶衍射表征。结果表明：1（CCDC: 1 445 377）属单斜晶系,P21/c空间群,晶胞参数a=1.393 2(6) nm, b=1.097 3(5) nm, c=1.933 7(8) nm, β=110.219(9) ,V= 2.77 4(2) nm³, Z=4, Dc=1.498 g·cm^-3, F(000)=1 264, R₁=0.028 8, wR₂=0.064 6。中心Sn为五配位三角双锥构型。研究了1的荧光性质、热稳定性、电化学性质和体外抗癌活性。结果表明:1在100 ℃下较稳定; 1在400 nm(λ_ex=320 nm)处有弱荧光峰;c(1)=5 μg·mL^-1时,对HeLa细胞株增殖的抑制率为93.70%。     

2,4-/2,6-二氨基甲苯在D151树脂上的吸附分离

从10种树脂中筛选出D151树脂对2,4-二氨基甲苯和2,6-二氨基甲苯的吸附分离及其热力学性质进行了研究。 测定了吸附等温线,Freundlich模型对实验的拟合度大于Langmuir模型,其相关系数大于0.99。 热力学研究结果表明,在293～313 K条件下,初始质量浓度为60～80 g/L时,2,4-二氨基甲苯的吸附焓变为-4.3490～-5.7558 kJ/mol,自由能变为-0.2911～-1.0346 kJ/mol,吸附熵变为-12.965～-16.150 J/(mol·K);而2,6-二氨基甲苯的吸附焓变为-2.9645～-3.6054 kJ/mol,自由能变为-0.1610～-0.6384 kJ/mol,吸附熵变为-7.939～-11.005 J/(mol·K)。 进一步研究了D151树脂对二氨基甲苯的动态吸附分离,可以将2,6-二氨基甲苯含量从20%提高至99.93%,将2,4-二氨基甲苯含量从80%提高至99.42%。     

Kinetics and Mechanism of Exothermic First-stage Decomposition Reaction of 2,6-Bis （2,2,2-trinitroethyl）glycoluril

The thermal behavior, mechanism and kinetic parameters of the exothermic first-stage decomposition of the title compound in a temperature-programmed mode were investigated by means of DSC, TG-DTG and IR. The reaction mechanism was proposed. The kinetic model function in differential form, apparent activation energy(Ea) and pre-exponential factor(A) of this reaction are (3/2)(1-a)[-ln(1-a)]1/3, 185.52 kJ/mol and 1017.78 s-1, respectively. The critical temperature of the thermal explosion of the compound is 201.30 ℃. The values of ΔS≠, ΔH≠ and ΔG≠ of this reaction are 72.46 J/(mol · K), 175.1 kJ/mol and 141.50 kJ/mol, respectively.     

Synthesis and Thermal Behavior of 1,8-Dihydroxy- 4,5-dinitroanthraquinone Manganese Salt

A novel energetic combustion catalyst, 1,8-dihydroxy-4,5-dinitroanthraquinone manganese salt （DHDNEMn）, was synthesized by virtue of the metathesis reaction in a yield of 91%, and its structure was characterized by IR, element analysis and differential scanning calorimetry（DSC）. The thermal decomposition reaction kinetics was studied by means of different heating rate DSC. The results show that the apparent activation energy and pre-exponential factor of the exothermic decomposition reaction of DHDNEMn obtained by Kissinger＇s method are 162.3 kJ/mol and 1011.8 s^-1, respectively. The kinetic equation of major exothermic decomposition reaction of DHDNEMn is dα/dT= 10^118/β 2/5（1-α）[-ln（1-α）[-ln（1-α）]^3/5 exp（-1.623×10^5/RT）. The entropy of activation（△S^≠）, enthalpy of activation（△H^≠） and free energy of activation（A△G^≠） of the first thermal decomposition are -24.49 J·mol^-1·K^-1, 185.20 kJ/mol and 199.29 kJ/mol（T=575.5 K）, respectively. The self-accelerating decomposition temperature（TSADT） and critical temperature of thermal explosion（Tb） are 562.9 and 580.0 K, respectively. The above-mentioned information on the thermal behavior is quite useful for analyzing and evaluating the stability and thermal safety of DHDNEMn.     

Synthesis,crystal structure and thermal behavior of 4-amino-3,5-dinitropyrazole copper salt

A novel energetic combustion catalyst, 4-amino-3,S-dinitropyrazole copper salt （[Cu（adnp）2（H2O）2]）, was synthesized in a yield of 93.6% for the first time. The single crystal of [Cu（adnp）2（H2O）2] was determined by single crystal X-ray diffraction. It crystallizes in a triclinic system, space group p^-1 with crystal parameters a = 5.541（3） A, b = 7.926（4） A, c = 10.231（5） A,β = 101.372（8）°, V = 398.3（3） A3, Z = 1, μ = 1.467 mm^-1, F（0 0 0） = 243, and Dc = 2.000 g cm^-3. The thermal behavior and non-isothermal decomposition reaction kinetics of [Cu（adnp）2（H2O）2] were studied by means of different heating rate differential scanning calorimetry （DSC）. The kinetic equation of major exothermic decomposition reaction for [Cu（adnp）2（H2O）2] was obtained. The entropy of activation （△S≠）, enthalpy of activation （△H≠）, free energy of activation （△G≠）, the self-accelerating decomposition temperature （TSADT） and the critical temperature of thermal explosion （Tb） are 59.42 j mol^-1 K^-1, 169.5 kJ mol^-1, 1141.26 kJ mol ^-1 457.3 K and 468.1 K, respectively.     

Studies on Adsorption Behavior and Mechanism of Copper（ Ⅱ ） onto Amino Methylene Phosphonic Acid Resin

IntroductionThe adsorption ability of the functional poly-mer used to enrich metal ions is strong and the op-eration of the functional polymer is convenient.The polymer having adsorbed metal ions can be re-covered by means of an acid or an alkaline solutionand the recovered polymeric material can bereused.The adsorption ability of the polymer withvarious functional groups is different for differentmetals.Because nucleophilic atoms such as oxy-gen,nitrogen,sulphur and phosphorous atoms cancoord…     

3,4-二硫方酸芳香性和气相酸性的理论研究

在RHF/6-311G^**,RHF/6-311+G^**和B3LYP/6-311+G^**水平优化得到3,4-二硫方酸(3,4-二巯基-3-环丁烯-1,2-二酮)三种平面构象异构体的平衡几何构型.用MP2(Full)/6-311G^**//RHF/6-311G^**方法计算单点能量,发现ZZ型异构体是能量最低构象,且ZZ和ZE型能量非常接近.用优化的最稳定构象ZZ型异构体在RHF/6-311G^**//RHF/6-311G^**,RHF/6-311G^**//RHF/6-311G^**,MP2(Full)/6-311G^**//RHF/6-311G^**和B3LYP/6-311G^**//B3LYP/6-311G^**水平计算其气相酸性(ΔG⁰)和同键反应芳香性稳定化能(HASE).用基团加和法(Group Increment Approach)在RHF/6-311G^**//RHF/6-311G^**和B3LYP/6-311G^**//B3LYP/6-311G^**水平计算其磁化率增量(Λ).计算结果表明,标题化合物的同键反应芳香性稳定化能和磁化率增量均为负值,表明它具有芳香性,实现了标题化合物芳香性的几何、能量和磁性的判定.     

Crystal Structure and Thermochemical Properties of 2-Pyrazine Carboxylate Lithium Monohydrate [Li(pyza)(H2O)]n(s)(pyza=2-Pyrazine Carboxylate)

A 2-pyrazine carboxylate lithium monohydrate [Li(pyza)(H₂O)]_n was synthesized in a mixed solution of redistilled water and anhydrous ethanol. X-Ray crystallography was applied to characterizing its crystal structure. Low temperature molar heat capacities were measured in a temperature range of from 78 K to 400 K with a precision automatic adiabatic calorimeter. Two polynomial equations of experimental molar heat capacity as a function of temperature were obtained by the least-squares method. The smoothed molar heat capacities and thermodynamic functions of the compound were calculated based on the fitted polynomial equations. In accordance with Hess's law, a reasonable thermochemical cycle was designed based on the preparation reaction of the target compound. The standard molar enthalpies of dissolution for the reactants and products of the designed thermochemical reaction were measured by an isoperibol solution-reaction calorimeter, and the enthalpy change of the reaction was obtained, i.e.,Δ_rH_m^θ=-(30.084±0.329) kJ/mol. The standard molar enthalpy of the formation of the target compound was determined as Δ_fH^θ_{m{[Li(pyza)(h2o)]n(s)}}=-(260.844±1.178) kJ/mol based on the enthalpy change of the reaction and standard molar enthalpies of the formation of other reactants and products. In addition, UV-Vis spectroscopy and the data of the refractive indexes were used to confirm whether the designed Hess thermochemical cycle was reasonable and reliable.     

明胶/Fe2S3纳米生物复合物形成反应的热力学及明胶构象变化

在pH=7.40条件下,采用一锅化学反应法制得水溶性明胶/Fe₂S₃纳米生物复合物,扫描电镜照片显示Fe₂S₃颗粒为棒状.根据吸光度与Fe₂S₃浓度关系,由Benesi-Hildebrand方程计算了不同温度下反应的形成常数K (293 K: 14.47×10² L·mol^-1; 297 K: 9.24×10² L·mol^-1; 309 K: 1.70×10² L·mol^-1)及对应温度下反应的热力学参数(Δ_rG_m = -17.88/-16.68/-13.09 kJ·mol^-1; Δ_rH_m = -105.57 kJ·mol^-1; Δ_rS_m = -299.28 J·K^-1·mol^-1),结果表明明胶/Fe₂S₃纳米生物复合物的形成反应是自发的放热过程,且为焓驱动.傅里叶变换红外光谱表明,Fe₂S₃主要与明胶大分子肽链中的酰胺键结合;对红外光谱进行去卷积拟合,结果表明:明胶蛋白质的 α-螺旋含量减少,β-折叠含量明显增加.结合紫外和红外光谱测试结果对复合物的形成机理作了初步的推测:首先Fe³⁺与明胶大分子中的酰胺键结合形成明胶/Fe³⁺复合物,然后S^2-与明胶/Fe³⁺中的Fe³⁺形成明胶/Fe₂S₃复合物.     

Three New Compounds Based on 4,4'-Azo-1,2,4-triazol-5-one: Synthesis,Crystal Structure and Thermal Properties

A series of guanidine salts of 4,4'-azo-1,2,4-triazol-5-one with guanidine(1), aminoguanidine(2), diaminoguanidine(3) and triaminoguanidine(4) was prepared. Compounds 2-4 were characterized by infrared(IR) spectroscopy, elemental analysis and single-crystal X-ray diffraction. Thermal decomposition processes of compounds 1-4 were investigated by differential scanning calorimetry(DSC), and all the compounds showed good thermal stability up to 190℃. Moreover, these four guanidine salts are more unstable with the increasing number of amino groups. Thermal stability parameters(T_e,0 and T_b) and thermodynamic functions(ΔS^≠, ΔH^≠ and ΔG^≠) for compounds 1-4 were calculated. The constant-volume combustion heats(Δ_cU) for compounds 2-4 were determined and tended to increase with the increase of the number of amino groups. The calculated standard molar enthalpies of formation(Δ_fH⁰m) of compounds 2-4 are -541.04, -178.67 and -83.08 kJ/mol, respectively. The impact sensitivities results indicate that these four energetic salts are less sensitive than 1,3,5-trinitrotriazacyccohexane(RDX) and 1,3,5,7-tetranitrotetraqza-cyclo-octane(HMX).