人全血中锶元素的分布及血浆中锶元素的形态分析

建立了基于液相色谱-电感耦合等离子体质谱(LC-ICP-MS)联用定量分析血浆中锶元素形态的方法,方法检出限为0.3 ng/mL,无机锶加标回收率为88%~97%,利用LC-ICP-MS分析,无机锶质量浓度在1.0~50.0μg/L之间时,线性回归系数r大于0.999。通过湿法消解,对73份人血和血浆用电感耦合等离子体质谱(ICP-MS)测定得出全血锶平均含量为38.1 ng/mL,血浆平均锶含量为35.8 ng/mL,说明全血中绝大部分锶存在于血浆中。通过LC-ICP-MS对血浆锶进行形态分析得出无机锶平均含量为10.2%,随色谱流出的有机锶平均含量为18.7%,而未随色谱流出的有机锶平均含量为71.1%,因此可推断摄入人体的锶主要以有机锶的形式发挥其生理作用。     

高效液相色谱-电感耦合等离子体质谱法快速测定天然水中无机砷的形态

建立了高效液相色谱-电感耦合等离子体质谱联用技术快速测定天然水中无机As形态的分析方法。采用Capcell PAK C18色谱柱分离As3+和As5+,5 min内可完成色谱分离,缩短了分析时间。在优化条件下,方法检出限可达到0.11μg/L和0.12μg/L,可满足天然水样品中无机砷形态的分析要求。研究了As形态标准溶液在不同保存条件下的形态稳定性问题,确定了无机As形态工作标准溶液和野外天然水样品采集和保存的最佳条件和时间。     

稀土对管线钢中碳化物溶解与析出行为的影响

以X80管线钢为研究对象,研究了稀土对含铌钢奥氏体化与析出行为的影响。利用热力学固溶度积公式,计算了铌碳化物的溶解温度;借助显微组织观察与硬度测试,对比分析了稀土对高温下奥氏体晶粒粗化及不同温度淬火回火后硬度的影响;通过热模拟实验并利用透射电镜,研究了稀土对实验钢在热变形过程中铌碳氮化物析出行为的作用机制。结果表明:稀土元素的加入降低了碳氮化物的固溶温度,促进了Nb(C,N)等第二相粒子的固溶,稀土能够促进热变形过程中Nb(C,N)的析出,从而提高铌元素的析出强化效果。     

二维TiC层表面H2的化学吸附与物理吸附

第一性原理计算研究发现由于二维TiC单原子层具有高的比表面积与大量的暴露在表面的Ti原子,其是一种非常有潜力的储氢材料.计算结果显示H2可以在二维TiC单原子层表面进行物理吸附与化学吸附.其中化学吸附能为每个氢分子0.36 eV,物理吸附能是每个氢分子0.09 eV.覆盖度为1和1/4层(ML)时,H2分子在二维TiC单原子层表面的离解势垒分别为1.12和0.33 eV.因此,除了物理吸附与化学吸附,TiC表面还存在H单原子吸附.最大的H2储存率可以达到7.69％(质量分数).其中,离解的H原子、化学吸附的H2、物理吸附的H2的储存率分别为1.54％、3.07％、3.07％.符合Kubas吸附特征的储存率为3.07％.化学吸附能随覆盖度的变化非常小,这有利于H2分子的吸附与释放.     

计算机模拟研究Pu~(4+)在人体血浆中的分布

建立了由多种金属离子和小分子配体组成的多相人体血浆热力学平衡模型。模拟研究了Pu4+在血浆的形态分布及二乙三胺五乙酸(DTPA)和CO32-、Citrate3-浓度对细胞液中Pu4+形态分布的影响。血浆中的低浓度Pu(Ⅳ)易以Pu(OH)4(aq)的形态蓄积在肝脏中,钚浓度升高则形成沉淀Pu(OH)4(s)难以排出。在[DTPA]=2.5×10-5mol·L-1时,血浆中水溶性小分子[Pu(OH)DTPA]2-含量达到最高并保持稳定。酸性条件下随着[Citrate3-]的升高,血浆中Pu4+与Citrate3-结合形成可溶性的[PuCitrate2]2-和[PuCitrate]+离子化合物。[DTPA]4.6×10-5mol·L-1时,血浆中的DTPA以与Ca2+、Mg2+结合的[CaHDTPA]2-、[Ca2DTPA]-、[CaDTPA]3-、[MgHDTPA]2-、[MgDTPA]3-小分子结合态为主。     

Effect of Molecular Weight on the Properties of Poly（butylene succinate）

Poly（butylene succinate） （PBS） with different molecular weight was synthesized from 1, 4-butanediol and succinic acid by direct melt condensation. The synthesized PBS was identified by IH-NMR and FTIR spectrometry. The molecular weight was calculated from the intrinsic viscosity, and its value was between 20000 and 70000. The crystallization behavior and crystal morphology as function of molecular weight were investigated by DSC and PLM, respectively. The mechanical properties and hydrolytic degradation behaviors related with change of molecular weight were also studied in this work. The results demonstrated that the properties of PBS were determined by both molecular weight and crystallization properties （crystallinity as well as crystal morphology）. Our work is important for the design and preparation of PBS with proper molecular weight for its practical application.     

Morphology Evolution of Poly（vinylidene fluoride） Membranes during Supercritical CO2 Assisted Phase Inversion

A supercritical carbon dioxide（Sc CO2） assisted phase inversion was developed to produce microporous poly（vinylidene fluoride）（PVDF） membranes whose morphology characteristics arise from both liquid-liquid demixing and solid-liquid demixing（crystallization）. This result was confirmed by Fourier transform infrared spectroscopy（FTIR）, from which both α and β crystals were found. As revealed by contact angle experiment, the PVDF membranes prepared via Sc CO2 assisted phase inversion were more hydrophobic compared with the control membrane produced via conventional immersionprecipitation technique. In particular, the sample with 15 wt% PVDF prepared at 45 °C and 13 MPa exhibited a contact angle of 142°, which was mainly caused by the multilevel micro- and nano- structure. The effects of polyethylene glycol（PEG）, polyvinyl pyrrolidone（PVP） and lithium chloride（Li Cl） on the structures and crystal form were investigated. PVP promoted the formation of β phase crystal form, while PEG boosts the evolution of α phase. Li Cl restrained the crystallization degree of PVDF membrane under Sc CO2.     

Influence of different inorganic salts on crystallization-driven morphological transformation of PCL-b-PEO micelles in aqueous solutions

Different inorganic salts, including NaSCN, NaCl, MgCl2 and Na2SO4, were added into the aqueous solution containing poly(ε-caprolactone)-b-poly(ethylene oxide)(PCL-b-PEO) semicrystalline micelles. The effects of inorganic salt on the micellar size and morphology were investigated with TEM and DLS. It is found that addition of NaSCN leads to increase of the micellar size, but the micelles remain to be spherical. By contrast, the other three inorganic salts can induce sphere-to-cylinder or sphere-to-lamella transformations of the PCL-b-PEO semicrystalline micelles. The alteration rate of the micellar size with the time after addition of the inorganic salts decreases in the following order: Na2SO4 NaCl ≈ MgCl2 NaSCN. These results were interpreted in terms of the "salting-out" ability of the cations and anions. The anions SO42- and Cl- have a stronger "salting-out" ability, driving the morphological transformations of the micelles and leading to a rapid change in micellar size. By contrast, SCN- has a weaker salting-out" ability. The cations Na+ and Mg2+ may associate with the PEO blocks, leading to a "salting-out" effect as well. However, the "salting-out" ability of cations is weaker than that of SO42- and Cl- anions, and the "salting-out" abilities of Na+ and Mg2+ are similar.     

杜仲叶水煎及醇提液中无机元素赋存形态分析

通过水煎及醇提法对杜仲叶中铁、锌、铜、锰、钾、钠、钙和镁8种无机元素进行提取,分别用微孔滤膜、D101大孔树脂、732阳离子树脂、D402螯合树脂将无机元素分为初级形态及次级形态。采用环己烷-正丁醇分配体系模拟人体肠胃条件将无机元素分为脂溶态和水溶态,用火焰原子吸收光谱法(FAAS)对各种形态的无机元素进行测定。结果表明:杜仲叶醇提液中各无机元素提取率均高于水煎液;杜仲叶醇提液中8种无机元素的提取率为6.61%~89.30%;次级形态分析参数表明各无机元素均以某种次级形态为主的多种形态共存于可溶态溶液中。该法测定各元素的回收率为98.99%~104.0%,相对标准偏差在0.35%~1.11%之间,具有良好的精密度和准确度。     

XANES技术探究酸处理对义马煤中硫形态及其热变迁行为的影响

利用XANES技术研究了酸处理对义马煤的比表面积、体相及表面硫形态分布和热解过程中硫变迁行为的影响。结果表明,由于酸处理过程中部分镶嵌于有机质中的矿物质被脱除导致部分闭合孔打开,煤的比表面积有所增大。HCl-HF和HCl-HF-HNO_3处理脱除了煤中大部分矿物质和无机硫,由于HNO_3的强氧化性,YMN中亚砜和砜硫化物的相对含量均高于YMR和YMD。相比煤样体相,酸处理过程对表面形态硫的分布产生了更为明显的影响。酸处理煤样热解含硫气体释放量减少,但由于大部分碱性矿物质的脱除和煤中易分解形态硫相对含量的增加,含硫气体释放率增加。不同形态硫之间的内部转化使得酸处理煤焦中主要形态硫的分布更为均匀。通过HCl-HF-HNO_3处理可以有效地脱除煤中矿物质及无机硫,并改变煤中形态硫分布,从而为高灰分、富含黄铁矿的高硫煤的利用提供指导。