超临界流体色谱与气相色谱-质谱联用测定卷烟主流烟气中醛酮类化合物的研究

建立了一种卷烟主流烟气中醛酮类香气化合物的超临界流体色谱/气相色谱-质谱测定方法。将捕集卷烟主流烟气粒相物的剑桥滤片用超临界流体萃取醛酮类香气成分后,通过配备高效分离柱的超临界流体色谱(SFC)先对香气成分进行划段,分离后的各段馏分再用GC-MS分析。结果表明:经SFC分离后的各段化合物之间基本不重叠,解决了GC-MS峰容量有限的问题,且分离出的醛酮类香气成分数量远多于直接进样分析法;样品直接进样后经GC-MS分析仅鉴定出29种醛酮类化合物,其中醛类7种、酮类22种;而经SFC分段后再用GC-MS分析,可鉴定出57种醛酮类化合物,包括13种醛类和44种酮类。3种不同焦油量卷烟主流烟气中醛酮类化合物种类和含量存在较大差异,每种卷烟主流烟气中分别含有不同特有醛酮类化合物。该研究为卷烟主流烟气中醛酮类香气成分的测定提供了新方法。     

Syntheses,Crystal Structures and Photoluminescence of Three Complexes Based on 3,5-(3-Carboxybenzyloxy)benzoic Acid

Three stable coordination polymers(CPs) assembled by 3,5-(carboxybenzyloxy)-benzoic acid(H3 L) and 1,10-phenanthroline(phen), namely, [Zn(HL)(phen)]n(1), [Cd(HL)(phen)]_n(2) and [Co(HL)(phen)]_n(3), have been synthesized under hydrothermal conditions. Their structures have been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, infrared(IR) spectroscopy and powder X-ray diffraction(PXRD). Investigation on crystal structure indicates that complexes 1 ～ 3 exhibit similar architecture. In these complexes, metal ions coordinate with H3 L and phen ligands, forming infinite 1 D chains. Then the adjacent chains combine together through intramolecular hydrogen-bonding interactions, generating 2 D supramolecular architectures. In addition, complexes 1～3 present excellent thermal stabilities and 1 and 2 exhibit strong luminescent emission bands at room temperature.     

HS/GC-MS法对卷烟包装材料中挥发性有机化合物的检测

建立了一种用于测定卷烟包装材料中挥发性有机物(VOCs)的分析方法.采用三醋酸甘油酯为基质,利用顶空技术对样品进行前处理,并与气相色谱质谱(GC-MS)联用,用离子选择对17种挥发性有机物进行了定量分析.在优化的实验条件下,方法线性关系良好,17种挥发性有机物的相关系数均大于0.999,检出限为0.30 ～18 μg/m2,比全扫描的检出限低1 ～3个数量级.17种挥发性有机物的回收率为90% ～101%,相对标准偏差小于3.67%.该法简便、快速、重复性好、定性定量准确,适于大批卷烟包装材料中挥发性有机化合物的检测.     

烟丝含水率对其燃烧性的影响研究

采用同步热分析技术考察了不同湿度下平衡后的烟丝燃烧性。结果表明:1烟丝含水率随着平衡湿度的增加而增加,并存在一定的线性相关;2通过比较每一阶段的失重率可知,烟丝不同含水率对其燃烧和热解反应的各个阶段有一定影响,失重率随着平衡湿度变化的转折点在平衡湿度50%~60%之间;3烟丝的燃烧特性指数Sn随着平衡湿度的增加而减小,平衡湿度与烟丝含水率、平衡湿度与平均燃烧速度间呈显著正相关,着火温度与燃烧特性指数间呈显著负相关,而平衡湿度与燃烧特性指数Sn无显著的相关性。     

网状钼酸铋的可见光催化活性

采用无助剂、无模板的水热法成功合成网状Bi₂MoO₆. pH值对这一形貌的形成起重要作用. 所制备的网状Bi₂MoO₆样品表现出优异的可见光催化活性,其光催化活性比固相法合成的块状Bi₂MoO₆样品高得多.     

一个基于2-(2-羧基苯基)-1H-咪唑并[4,5-f][1,10]邻菲啰啉配体的二维铅(Ⅱ)配合物的水热合成及晶体结构

在水热条件下,利用邻菲啰啉衍生物2-(2-羧基苯基)-1H-咪唑并[4,5-f][1,10]邻菲啰啉(HL)和Pb(NO3)2反应合成了一个配合物[PbL2]n(1),并用红外、元素分析和X射线单晶衍射对其结构进行了表征。配合物1属于单斜晶系,空间群为P21/c,晶胞参数a=1.345 9(9)nm,b=0.709 4(5)nm,c=3.265 5(2)nm,β=99.6260(10)°,V=3.074 0(4)nm3,Z=4,C40H22N8O4Pb,Mr=885.85,Dc=1.914 g·cm-3,μ(MoΚα)=5.551 mm-1,F(000)=1728,GOOF=1.038,R=0.027 0,wR=0.058 1,其中5 067个可观测点(I>2σ(I))。结构分析表明配合物1为二维层状结构。此外,对配合物的热稳定性和发光性质也进行了研究。     

基于3,5-二((4'-羧基苄基)氧)苯甲酸和4'-(4-吡啶基)-2,2':6',2"-三联吡啶为混合配体的两个配合物的水热合成与晶体结构

在水热条件下,以3,5-二((4''-羧基苄基)氧)苯甲酸(H₃bcb)和4''-(4-吡啶基)-2,2'':6'',2"-三联吡啶(PYTPY)为混合配体构筑了2个过渡金属配合物[Co(H₂bcb)₂(PYTPY)]_n(1)和[Mn(H₂bcb)₂(PYTPY)]_n(2),利用元素分析、红外光谱以及单晶X射线衍射表征其结构。分析表明配合物1和2为一维链状结构。此外,2个配合物展示了优良的热稳定性。磁化率的测试结果表明,配合物1和2在2 K和8 K以下时展示了反铁磁相互作用。     

以2,4′-联苯二羧酸及咪唑并[4, 5-f][1, 10]邻菲咯啉为配体的钴(Ⅱ)、锰(Ⅱ)配合物的水热合成及晶体结构

在水热条件下, 以2, 4′-联苯二羧酸(2, 4′-H₂bpdc)和咪唑并[4, 5-f][1, 10]邻菲咯啉(L)为配体构筑了两种配合物{[Co(2, 4′-bpdc)(L)(H₂O)]·H₂O}_n (1)和[Mn(2, 4′-bpdc)(L)(H₂O)]_n (2), 并利用元素分析、X-射线单晶衍射和热重分析对其结构进行了表征。配合物1具有一维链状结构, 配合物2展示了一维双链结构, 两个配合物都通过分子间氢键和π-π相互作用形成三维网状结构。     

发散型准直器限束孔应用于被动散射质子放疗可行性研究

被动散射质子放疗（Passive Scattering Proton Therapy,PSPT）是质子治疗的主要技术之一,束流通过准直器限束孔（Aperture）时因边缘散射效应导致患者体内剂量分布偏离理想状态。使用蒙特卡洛软件TOPAS（TOol for PArticle Simulation）对质子束流经过发散型与传统型准直器限束孔后进入水模体中的过程建模,分析两种准直器的边缘散射效应对剂量及中子能谱分布的影响,分别测试70,110,160,200,230,250 MeV能量下的质子束流,发现传统Aperture在70 MeV的质子束下边缘散射效应最明显,在距水箱表面0.5 cm深度处横向剂量曲线平坦度、均匀度分别达到4.63%,108.05%,随着深度增加边缘散射效应逐渐减弱,在布拉格峰位置处接近消失。使用发散型准直器限束孔后,在70 MeV下平坦度、均匀度分别降至1.28%,101.31%,对于100,160,200 MeV质子束均有不同程度改善。对于能量接近250 MeV的质子束,发散型准直器限束孔设置下横向剂量曲线并无优势。边缘散射效应导致的剂量不均随水深增加而减弱,对于各个能量质子,使用发散型准直器限束孔后次级中子减少。研究结果表明,发散型准直器限束孔应用于PSPT效果显著,为进一步应用于临床提供数据支撑。Passive Scattering Proton Therapy (PSPT) is one of the main technologies for proton radiation therapy. The dose distribution in the patient deviates from the ideal state due to the edge scattering effect when the beam passes through the aperture. In this paper, TOPAS, a Monte Carlo software, was used to simulate the passive scattering treatment head. The influence of the edge scattering effect of the two aperture sets on the dose distribution was compared. The proton beam at 70, 110, 160, 200, 230 and 250 MeV was tested respectively. We found that the scattering effect of the conventional aperture is most obvious at 70 MeV, and the flatness and hetergeneity of the lateral dose curve at the inlet of 0.5 cm of the tank reach 4.63%, 108.05%, respectively. The dose shift caused by the edge scattering effect decreases with increasing water depth and disappears at the Bragg peak. After using the divergent aperture, the flatness and uniformity at 70 MeV are reduced to 1.28% and 101.31%, respectively, and the 100, 160, and 200 MeV proton beams are improved in different extents. For a proton beam with an energy close to 250 MeV, there is no advantage in the lateral dose curve of the divergent aperture. For all energy protons, the secondary neutrons are reduced with divergent aperture. The results show that the divergent aperture is effective for PSPT and this study provides data support for further application in clinical practice.     

二维铅配合物[Pb2(C8H4O4)2(C19H12N4O)2]n·3.5nH2O的水热合成、晶体结构与荧光性质研究

In the title compound, [Pb₂(C₈H₄O₄)₂(C₁₉H₁₂N₄O)₂]_n·3.5nH₂O(1), has been synthesized by the hydrothermal assembly of 1,4-benzenedicarboxylate and 4-(1H-1,3,7,8-tetraazacyclopenta[l]-phenanthren-2-yl)phenol(TCPP) with lead acetate. Elemental analysis, X-ray crystal structure analysis, IR spectrum, thermogravimetric analysis and luminescence property were carried out for the structural determination and characterization of the title compound. Compound 1 crystallizes in triclinic, space group P1 with a=1.013 54(10) nm, b=1.104 84(11) nm, c=1.210 05(12) nm, α=76.812 0(10)°, β=74.814 0(10)°, γ=86.030 0(10)°, V=1.273 1(2) nm³, Pb₂C₅₄H₃₉N₈O_13.5, M_r=1 430.31, Z=1, D_c=1.866 g·cm^-3, μ=6.680 mm^-1, F(000)=691, R=0.027 3 and wR=0.068 7 for 4 042 observed reflections (I>2σ(I)). The compound 1 exhibits two-dimensional network structures, which are further stacked through π-π interactions and hydrogen bonds to form three-dimensional supramolecular polymer. Solid-state luminescent spectrum of the compound 1 indicates intense fluorescent emission. CCDC: 748883.