加速溶剂萃取-高效液相色谱-串联质谱法同时检测鱼肉中喹诺酮、磺胺与大环内酯类抗生素

建立了加速溶剂萃取(ASE)-高效液相色谱-串联质谱联用法同时检测鱼肉中22种抗生素药物残留的分析方法。样品经ASE提取,HLB固相萃取柱净化后进入高效液相色谱-串联质谱仪分析。对ASE的萃取条件进行优化,并采用XTerraMSC18柱对药物进行分离,以甲醇-乙腈(体积比1∶1)为色谱流动相A,以0.3%(体积分数)甲酸水溶液(含0.1%甲酸铵,pH=2.9)为流动相B。22种喹诺酮、磺胺和大环内酯类抗生素药物在加标水平为20、100μg/L时的回收率分别为72%～120%与66%～114%,相对标准偏差(RSD,n=5)分别为1.9%～16%与0.7%～10%,方法的检出限为0.02～0.6μg/kg。结果显示所建立的方法精密度好,准确度高,可满足同时对鱼肉样品中多种喹诺酮、磺胺和大环内酯类抗生素残留进行定性及定量分析的要求。     

二氧化碳化学:二氧化碳的催化转化反应

二氧化碳既是温室气体的主要成分又是储量丰富且可再生的碳资源,研究二氧化碳的化学转化和利用有着重要意义。基于二氧化碳与催化剂的弱相互作用以及催化活化原理,通过采用环境友好的反应介质(如高密度二氧化碳、聚乙二醇等)及催化剂的设计、分离和循环利用等策略,设计并合成了单组分和双组分的功能化高效催化剂用于合成有机碳酸酯、脲、噁唑啉酮和喹唑啉二酮类化合物,并相应建立了具有重要工业应用价值的合成新方法以及环境友好的新工艺。以二氧化碳为合成子的精细化工中间体合成不但丰富了有机化学的合成方法学,也为解决日渐严重的环境问题提供潜在的新方法。在此,对本课题组近二年来在二氧化碳化学尤其是二氧化碳催化转化方法方面的研究成果做一小结。     

Evaluation of Thermal Hazard of Composite Modified Double-base Propellant by Microcalorimetery Method

<正>The thermal decomposition behavior of composite modified double-base(CMDB) propellant containing cyclotrimethylene trinitramine(RDX) was studied via a Calvet microcalorimeter at five different heating rates.The activation energy(E) and the pre-exponential factor(A) of two obvious exothermic processes were obtained by Kissinger's method and Ozawa's method.The entropy of activation(△A~≠),the enthalpy of activation(△H~≠),and the free energy of activation(△G~≠) of the first stage were calculated.To evaluate the thermal hazard of the RDX-CMDB propellant, the critical temperature of thermal explosion(T_b),the self acceleration decomposition temperature(T_(SADT)),the adiabatic decomposition temperature increment(△T_(ad)) and the time-to-explosion of adiabatic system(t) were presented as 145.3℃,138.15℃,1634 K and 583.71 s(n=0) and 586.28 s(n=1),respectively.     

Synthesis, Structure and Luminescence of Zn4.5Cu3 Heteronuclear Coordination Polymer Comprising Macrocyclic Oxamide and 5-Sulfosalicylic Ion

<正>The complex[Zn_(4.5)(SSA)_3(CuL)_3(H_2O)_6]_n was synthesized and structurally determined,where SSA is fully deprotonated 5-sulfosalicylic acid(CuL,H_2L=2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca- 7,13-dien).The title complex crystallized in the triclinic system with space group P1,a=1.19788(17) nm,b=1.4253(2) nm,c=2.2890(4) nm,α=90.211(2)°,β=93.076(2)°,γ=90.600(2)°.The complex displayed a 1D ladderlike chain.All these 1D chains were further interlinked via hydrogen bonds,resulting in a 2D architecture.The luminescent property of the compound was also discussed.     

Estimation of Critical Temperature of Thermal Explosion for Trinitromethyl Explosives by Non-isothermal DSC

Two general expressions and their six derived formulae for estimating the critical temperature(Tb) of thermal explosion for energetic materials(EMs) were derived from the Semenov’s thermal explosion theory and eight non-isothermal kinetic equations via reasonable hypothesis. We can easily obtain the values of the initial temperature(T0i) at which DSC curve deviates from the baseline of the non-isothermal DSC curve of EMs, the onset temperature(Tei), the exothermic decomposition reaction kinetic parameters and the values of T00 and Te0 from the equation T0i or ei=T00 or e0+α1βi+α2βi2+···+αL–2βiL–2, i=1, 2, ···, L and then calculate the values of Tb by means of the six derived formulae. The results obtained with the six derived calculating methods for six trinitromethyl explosives: bis(2,2,2- trinitroethyl-N-nitro) ethylene diamine(BTNEDA), 2,2,2-trinitroethyl-4,4,4-trinitrobutyrate(TNETB), bis(2,2,2- trinitroethyl) formal(BNTF), bis(2,2,2-trinitroethyl-nitramine)(BTNNA), 2,2,2-trinitroethyl-2,2,2-trinitroethyl-N- nitroamino acetate(TNTNNA) and tetrakis [2,2,2-trinitroethyl] orthoester(TTNOE) agree well with each other.     

溶剂萃取法提锂的研究进展

总结了采用溶剂萃取法在盐湖卤水中提取锂资源的三类萃取剂:酸性萃取剂、中性络合萃取剂和碱性萃取剂,分析了三类不同萃取剂在萃取锂工艺过程的优缺点,指出了溶剂萃取法从高镁锂比的盐湖卤水中萃取提锂尚待攻克的技术难题。     

查尔酮衍生物E-2-(甲氨基)-7-(3-(吡啶基)丙烯酰基)卓酮的合成(英文)

以2-乙酰基-7-(甲氨基)卓酮(1)为原料,经由与各种吡啶醛的Claisen-Schmidt缩合反应得到查尔酮衍生物E-2-(甲氨基)-7-(3-(吡啶基)丙烯酰基)卓酮(2～5).全部合成产物均为新化合物,未见文献报道;其结构均由红外光谱分析、1H核磁共振、质谱及元素分析得以证实.     

三元钴配合物[Co(NCS)_2(ql)_2](ql=喹啉)的合成及其晶体结构和荧光性质

合成了含异硫氰酸根和喹啉(ql)混合配体的钴配合物[Co(NCS)2(ql)2];利用红外光谱、紫外光谱和X射线单晶衍射等手段对其结构进行了表征;研究了配合物在室温下的荧光发射光谱特性.单晶结构解析结果表明,标题化合物属于单斜晶系,P21/c空间群,晶胞参数为:a=1.486 33(5)nm,b=0.844 44(3)nm,c=1.541 16(5)nm,β=92.093(2),V=1.933 0(2)nm3,Z=4,Dc=1.489 g/cm3,μ=1.116 mm-1,F(000)=884,R1=0.032 2,wR2=0.078 6.配合物中钴离子采用四配位的四面体配位构型,晶体堆积中通过π-π作用形成一维超分子结构.     

Enhanced two-photon emission in coupled metal nanoparticles induced by conjugated polymers

Interactions between noble metal (Ag and Au) nanoparticles and conjugated polymers as well as their one- and two-photon emission have been investigated. Ag and Au nanoparticles exhibited extraordinary quenching effects on the fluorescence of cationic poly(fluorinephenylene). The quenching efficiency by 37-nm Ag nanoparticles is ～19 times more efficient than that by 13-nm Au nanoparticles, and 9-10 orders of magnitude more efficient than typical small molecule dye-quencher pairs. On the other hand, the cationic conjugated polymers induce the aggregate formation and plasmonic coupling of the metal nanoparticles, as evidenced by transmission electron microscopy images and appearance of a new longitudinal plasmon band in the near-infrared region. The two-photon emissions of Ag and Au nanoparticles were found to be significantly enhanced upon addition of conjugated polymers, by a factor of 51-times and 9-times compared to the isolated nanoparticles for Ag and Au, respectively. These studies could be further extended to the applications of two-photon imaging and sensing of the analytes that can induce formation of metal nanoparticle aggregates, which have many advantages over the conventional one-photon counterparts.     

基于PEI的亚氨乙酸型复合螯合吸附材料IAA-PEI-SiO_2的制备及其螯合吸附特性

以偶联剂γ-氯丙基三甲氧基硅烷为媒介,将聚胺大分子聚乙烯亚胺(PEI)以偶合接枝的方式,接枝于微米级硅胶微粒表面,制得接枝微粒PEI-SiO2,然后以氯乙酸为试剂,通过亲核取代反应将亚氨乙酸(IAA)基团键合于硅胶微粒表面,形成了具有多齿配基的亚氨乙酸型螯合微粒IAA-PEI-SiO2。重点研究了螯合微粒IAA-PEI-SiO2的制备过程,初步探讨了其对重金属离子及稀土离子的螯合吸附特性。研究结果表明:接枝微粒PEI-SiO2与氯乙酸之间的亲核取代反应遵循SN2反应历程;反应温度较高或缚酸剂用量过多时,会促进氯乙酸的水解,减缓亲核取代反应,使亚氨乙酸的键合率下降;适宜的反应温度为60℃,适宜的缚酸剂NaHCO3用量是使体系中NaHCO3与氯乙酸物质的量之比为1∶1。与接枝微粒PEI-SiO2相比,螯合微粒IAA-PEI-SiO2对Cu2+及Eu3+的吸附容量大幅度提升,显示出强螯合吸附特性。