Synthesis, characterization and antitumor activity of rare earth （Y, La） substituted phosphotungstates containing 5-fluorouracil

Two rare earth substituted Keggin-type phosphotungstates containing 5-fluorouracil,K10C4H4FN2O2Y(PW11O39)2·10H2O(FYPW) and K9(C4H4FN2O2)2La(PW11O39)2·18H2O(FLaPW)were synthesized in aqueous solution,and the structures were characterized by Fourier transform infrared spectroscopy(FT-IR),element analysis,inductively coupled plasma spectrometry(ICP),X-ray powder diffraction(XRD) and 1 H nuclear magnetic resonance(NMR).Thermal analysis showed that the decomposition processes of the two compounds could be divided into three steps,the loss of crystal water,the decomposition of 5-fluorouracil unit and the decomposition of Keggin-type polyanions. The in vitro cytotoxicities against HEK 293,HeLa and HepG-2 cells were studied by methyl thiazolyl tetrazolium(MTT)assay.The results showed that FYPW and FLaPW had higher antitumor activities than 5-fluorouracil,C4H4FN2O2H2PW12O40·8H2O and rare earth substituted polyoxometalates K11Ln(PW11O39)2·nH2O(Ln=Y,La).It was concluded that introducing 5-fluorouracil and rare earth(Y or La)into its structure was a considerable way to enhance antitumor activities of polyoxometalates.     

4-硝基-4′-氟苯基重氮氨基偶氮苯双波长分光光度法测定镍

报道了新含氟显色剂4-硝基-4′-氟苯基重氮氨基偶氮苯与镍(Ⅱ)的显色反应。试验表明,在pH 8.6 Na2B4O7-HCl缓冲溶液、Tween-85存在下,试剂与镍(Ⅱ)形成4∶1的稳定紫红色络合物。最大吸收正峰为504 nm,负峰为424 nm;且在25 mL显色液中镍(Ⅱ)的量在0~4μg范围内符合比尔定律。在两最大正负吸收波长处分别进行单波长分光光度法测定,表观摩尔吸光系数分别为1.13×105,1.06×105L.mol-1.cm-1。再以424 nm为参比波长、504 nm为测量波长进行吸光度叠加的双波长光度法测定,表观摩尔吸光系数为2.17×105L.mol-1.cm-1。加入混合掩蔽剂NaF-硫脲,可消除常见共存离子的干扰。本法可用于测定多元素混合标准溶液和不锈钢中的镍(Ⅱ),回收率为96%~98%,混合标准溶液的测定值与认定值相一致。     

Synthesis and antitumor activities of rare earth substituted phosphotungstates containing 5-fluorouracil

Two novel rare earth substituted phosphotungstates containing 5-fluorouracil,K 9(C 4 H 4 FN 2 O 2) 2 Nd(PW 11 O 39) 2 ·25H 2 O(FNdPW) and K 9(C 4 H 4 FN 2 O 2) 2 Ce(PW 11 O 39) 2 ·23H 2 O(FCePW),were synthesized and characterized by elementary analysis,FT-IR spectra,X-ray powder diffraction and 1 H NMR.The thermal analysis showed that FNdPW decomposed at 210 and 493 oC,and FCePW decomposed at 223 and 471 oC,both of which had good thermal stabilities.MTT tests were performed to study the antitumor activities against HeLa cells and HepG-2 cells of FNdPW,FCePW,5-fluorouracil,C 4 H 4 FN 2 O 2 H 2 PW 12 O 40 ·8H 2 O and K 11 Ln(PW 11 O 39) 2 ·xH 2 O(Ln=Nd,Ce),and their cytotoxicities against HEK 293 cells.The results showed that FNdPW and FCePW possessed higher antitumor activities and lower cytotoxicities than those of 5-fluorouracil and C 4 H 4 FN 2 O 2 H 2 PW 12 O 40 ·8H 2 O,of which FNdPW exhibited the highest antitumor activates against HeLa cells(EC 50 =3.41×10-6 mol/L) and HepG-2 cells(EC 50 =6.24×10-6 mol/L).Thus the introduction of rare earth elements and 5-fluorouracil could significantly enhance antitumor effect of polyoxometalates.     

喷雾干燥法合成锂离子电池复合正极材料xLiFePO4.yLi3V2(PO4)3及性能研究

采用喷雾干燥和高温固相法合成了一系列xLiFePO4·yLi3 V2( PO4)3复合正极材料.电化学测试结果表明,0.95LiFePO4·0.05Li3 V2( PO4)3复合正极材料具有较高的比容量、优良的循环性能和倍率性能,在电压范围为2.0V～4.3V,0.1C,1C,5C条件下的放电容量分别为162.7,147.7和122.3 mAh·g-1.0.5LiFePO4·0.5Li3 V2(PO4)3和0.3LiFePO4·0.7Li3 V2 (PO4)3复合正极材料则表现出了良好的倍率性能,5C,10C充放电条件下容量保持率分别为:77％,73％,88％,82％.     

副产硫酸钙室温固相球磨制备氧化钙

以锰尾矿制备硫酸锰过程中副产硫酸钙为原料在室温下与碳酸氢铵进行固相球磨反应,制备出氧化钙的前驱体碳酸钙,然后将其煅烧得到氧化钙.分别考察了物料配比、球磨时间、球料质量比等因素对硫酸钙转化率的影响,采用X射线衍射和化学分析方法对产物进行了分析,并对室温固相球磨反应的机理进行了探讨.在物料配比(摩尔比)为3.5:1、球磨时间为40 min以及球料质量比为5:1时,硫酸钙的转化率可达到99.8%,将固相产物在1000℃热解1 h后所制备的氧化钙纯度为99.2%.室温球磨过程细化了反应物的颗粒尺寸,增加了反应物的接触面积,为引发反应提供了必要的能量,因此提高了化学反应的有效性.     

2-(5-溴-4-甲基-2-吡啶偶氮)-5-二甲氨基苯胺双波长叠加光度法同时测定钯和铑

以试剂2-(5-溴-4-甲基-2-吡啶偶氮)-5-二甲氨基苯胺(5-Br-4-CH₃-PADMA)为显色剂,建立了双波长叠加分光光度法同时测定铑和钯的新方法。结果表明:钯与5-Br-4-CH₃-PADMA在0.9~4.2 mol/L 高氯酸介质中,形成稳定络合物;而铑与5-Br-4-CH₃-PADMA在pH值为4.2~5.0的近中性介质中形成稳定络合物,络合物一旦形成则很稳定,向其中加入强酸酸化,该配合物不仅不分解,反而吸收峰红移,吸光度增大。研究还发现,铑、钯与5-Br-4-CH₃-PADMA形成的络合物,均呈现两个强弱不等的吸收峰,强峰分别位于605 nm和606 nm,弱峰分别位于558 nm和563 nm。在605 nm和562 nm处,其各自的强弱峰对应的吸光度之和与溶液中铑、钯的质量浓度具有良好的线性关系。铑、钯质量浓度分别在0~0.55 μg/mL 和0~1.04 μg/mL范围内符合比尔定律;利用双波长叠加的分光光度法测得铑、钯的表观摩尔吸光系数分别为ε_Rh=2.64×10⁵ L·mol^-1·cm^-1和ε_Pd= 1.40 ×10⁵ L·mol^-1·cm^-1,铑络合物的组成为n(Rh)∶n(5-Br-4-CH₃-PADMA) =1∶2,钯络合物的组成为n(Pd)∶n(5-Br-4-CH₃-PADMA)=1∶1。方法用于实际样品催化剂中铑和钯的同时测定,结果的相对标准偏差(RSD,n=6)分别为1.4%和4.9%,测定值与原子吸收光谱法测定值相一致。     

锌阳极的微观组织和腐蚀失效分析

通过分析失效锌阳极表面形成的约1 mm厚度的腐蚀产物层发现,腐蚀产物与基体结合牢固、不导电是导致阳极无法发挥保护作用的直接原因。锌阳极表面的腐蚀产物具有明显的分层结构,腐蚀产物形貌以片状产物居多,也有球状产物,片状产物主要为Zn₁₂（SO₄）₃Cl₃（OH）₅·5H₂O和Zn₄SO₄（OH）₆·5H₂O,球状产物主要为Zn₅（OH）₈Cl₂·H₂O;锌块中Pb、Cu、Fe含量（质量分数）略微超标,造成锌保护效率下降。当牺牲阳极受到杂散电流干扰,其表面会被快速极化呈钝化状态,以0.1mA·cm-2恒电流极化10 h,锌表面即发生严重钝化,失去其牺牲保护的作用。     

硫酸镍电解液净化除杂工艺研究

对硫酸镍电解液的萃取净化除杂进行了系统的研究。实验采用M5640对铜离子进行除杂,实验条件为:pH值为3.0,相比为1∶1,萃取剂体积浓度为15%,振荡时间5min,在此实验条件下铜离子的萃取率大于99.83%,其含量小于0.1mg·mL-1,已达到5N镍电解液标准。去除铜离子之后,采用P507对电解液进行除杂,在实验条件pH为4.0,相比为1∶1,萃取剂体积浓度为15%,振荡时间5min下,二价铁离子、锌离子、铅离子的萃取率分别为:99.93%,99.75%,84.01%,其含量分别为:0.10,0.21,0.30mg·mL-1,已达到5N镍电解液标准。在此之后再采用P507对电解液中钴离子进行去除,实验条件为:用氢氧化钠溶液均相制皂75%,提高待萃液当中钴离子的含量至4.19g.L-1,即Co/Ni为1/10。实验采取四级萃取,控制水相pH值在4～5之间。钴离子萃取率为74.92%,含量为14.88mg·mL-1,已达到5N镍电解液标准。     

镉(Ⅱ)-碘化钾-吖啶橙缔合体系光度法测定痕量镉

在pH3.6 NaAc-HAc缓冲溶液中,Cd2+与过量的KI和吖啶橙(AO)反应生成稳定的离子缔合物[AO]2[CdI4],体系吸光度明显增强,建立了分光光度法测定痕量镉的新方法。试验了酸度、试剂用量、表面活性剂、温度和时间的影响,确定了最佳测定条件。最大吸收峰位于484 nm,线性范围为0~0.4μg/mL,表观摩尔吸光系数为1.66×105L.mol-1.cm-1,检出限为6.82μg/L。大量的常见离子不干扰测定,MnO4-、Pb2+、Fe3+和Hg2+的干扰可采用抗坏血酸-巯基棉分离去除。方法用于测定河水中镉,结果与原子吸收光谱法一致。相对标准偏差为1.7%~2.0%(n=5),回收率为98%~100%。     

Effect of Lanthanum on Expression of Recombinant Allophycocyanin Gene in Pichia Pastoris

The methylotrophic yeast ,Pichia pastorishasbeen developed to be an outstanding host for the pro-duction of foreign proteins since its alcohol oxidasepromoter was isolated and cloned ,and its transforma-tion was first reported in 1985[1 ,2].This organismh…     

Rolling Contact Fatigue Properties of SAE 8620 Steel after Case Carburizing

Rolling contact fatigue(RCF)properties of SAE 8620 steel after case carburizing have been investigated under two contact stresses of 4.0and 5.5GPa.Results show that the RCF life ranges from 2.5×10~6 to 3×10~7 cycles under the contact stress of 5.5GPa,while it can be more than 1×10~8 cycles under the contact stress of 4.0GPa.The rated fatigue life L_(10)(lives with the 10%failure)is also drastically shortened from 9.8×10~6 to 5.4×10~5 cycles when the contact stress is increased from 4.0to 5.5GPa.Theoretical calculations and fractographs show that the maximum shear stress and the contact area increase with increasing the contact stress,making RCF tend to occur earlier.     

Phase Structure and Electrochemical Properties of RE-Mg Based Composite Hydrogen Storage Alloys

Rareearth basedAB5 typealloy ,akindofhy drogenstoragealloyusedasnegativeelectrodemateri alsofthenickel/metalhydride (Ni/MH )secondarybattery ,haseasyinitialactivation ,longcyclelifeandlowcost ,butstillasmalldischargecapacity ,poorhigh ratedischargeability(HRD)andpoorpropertiesatlowtemperature[1,2 ] .Therefore ,howtoincreaseitsdischargecapacityandtoimproveotherelectrochemi calpropertiesismeaningfulbothintheoryandinpracticalapplication .Mg basedhydrogenstorageal loysareremarkablebecauseofitsr…     

Synthesis, structures,thermal and magnetic properties of a series of lanthanide [Ln=Sm, Gd, Er, Yb] complexes with 4-quinolineacarboxylate

A series of lanthanide binuclear complexes, [Ln2(L)6(H2O)4]·2H2O (Ln=Sm(III), Gd(III), Er(III), Yb(III), HL=4-quinolineacarboxylic acid, were synthesized by reactions of corresponding rare earth salts with 4-quinolineacarboxylic acid at room temperature and were characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray diffraction. X-ray diffraction analyses showed that they exhibited the same binuclear architecture and crystallized in monoclinic system and P21/c space group. In four complexes, each metal center adopted nine-coordinated mode coordinated by nine O atoms from two H2O molecules and three carboxyls of three ligands, and HL showed three different coordination modes. The variable-temperature magnetic susceptibility showed that complex [Gd2(L)6(H2O)4]·2H2O performed very weak antiferromagnetic property at low temperature and exchange was almost paramagnetic at high temperature. Complexes [Er2(L)6(H2O)4]·2H2O and [Yb2(L)6(H2O)4]·2H2O performed dominating antiferromagnetic coupling.     

Luminescent properties of YVO4·xTa2O5:Eu3+

The samples of YVO4·xTa2O5:Eu3+(x=0.45,0.35,0.25,0.15,0.05)were synthesized by the conventional solid state reaction.The structure of the prepared sample was checked by the X-ray diffraction.XRD measurements at room temperature were confirmed that the prepared YVO4·xTa2O5:Eu3+ consisted of two phases。One phase was YVO4,which is tetragonal according with the JCPDS-Card(17-0341);the other phase was YTaO4,which is according with the JCPDS-Card(72-2018).The spectrum property of the sample was studied under the VUV.The effects of Ta doped on the luminescent properties of sample were investigated and it was found that some Ta doped could highlight the absorption of matrix in VUV region.The emission spectrum was dominated by the red peaks at 613 and 619 nm due to the electric dipole transition 5D0→7F2 of Eu3+.It indicated that Eu3+ occupied a site lacking inversion symmetry.There was one band peaked at 155 nm in the excitation spectrum of the sample,it could be assigned to the absorption of the host.     

5-(5-碘-2-吡啶偶氮)-2,4-二氨基甲苯双波长叠加分光光度法同时测定钴和钯

以试剂5-(5-碘-2-吡啶偶氮)-2,4-二氨基甲苯( 5-I-PADAT )做显色剂,建立了双波长叠加分光光度法同时测定钴和钯的新方法。研究发现,在0.6～2.4 mol/L HClO₄介质中,钯(Ⅱ)与5-I-PADAT反应形成稳定络合物,而在此高酸度下,钴(Ⅱ)则完全不能显色;在pH 3.6~10的缓冲介质中,钴(Ⅱ)与5-I-PADAT反应形成稳定络合物,钴络合物形成后以强酸酸化,提高酸度至0.6~3.0 mol/L HClO₄,可转变为另一种具有较高吸收特性质子化型体。研究还发现,钴(Ⅱ)、钯(Ⅱ)与5-I-PADAT形成的络合物,均呈现两个吸收峰,且吸收峰位置十分接近,强峰分别位于580和583 nm,弱峰分别位于532和543 nm。基于钴(Ⅱ)、钯(Ⅱ)与5-I-PADAT显色酸度的差异以及吸光度的加合性特点,采用双波长叠加,建立了分光光度法同时测定钴和钯的新方法。钴、钯质量浓度分别在0～0.4 μg/mL和0～1.0 μg/mL范围内服从比尔定律,表观摩尔吸光系数分别为2.17×10⁵ L·mol^-1·cm^-1和1.10×10⁵ L·mol^-1·cm^-1,灵敏度较单波长分别提高1.75和1.53 倍。方法应用于催化剂和矿样中钴和钯的同时测定,测定值与推荐值相一致,相对标准偏差(RSD,n=6)分别为0.50%～2.3%(钴)和1.0%～1.4%(钯)。     

黄铜表面富植酸钝化工艺研究

采用植酸(50%,质量分数)8 ml.L-1,双氧水(30%,质量分数)30 ml.L-1,硼酸5 g.L-1,聚乙二醇15 ml.L-1,添加剂4 g.L-1钝化液对冷轧HAl72-2.5-1黄铜带材进行钝化处理,探讨工艺条件(钝化温度、钝化时间和钝化液pH值)对富植酸钝化膜耐蚀性的影响。通过硝酸溶液点滴腐蚀试验对黄铜表面富植酸钝化膜的耐腐蚀性能进行研究。结果表明,富植酸钝化膜的最佳工艺条件为:钝化温度范围是35～40℃,pH值为2.5,钝化时间为60 s。SEM微观形貌显示,膜层表面平整,结构致密。失重试验结果表明:经富植酸处理的试样的平均腐蚀速率为0.0054 g.m-.2h-1,与重铬酸盐处理的试样的平均腐蚀速率(0.0040 g.m-.2h-1)相当,比未经钝化处理的试样的腐蚀速率(0.0376 g.m-2.h-1)低的多,说明采用富植酸钝化处理能对合金材料起到很好的保护作用。经过12 h的盐雾法试验显示:经重铬酸盐处理的试样表面有较多的褐色斑点,表面颜色不均匀,而经过富植酸处理的试样表面为金黄色,只有少量的腐蚀斑,说明采用富植酸处理的试样比采用重铬酸盐处理的试样具有更好的抗变色能力。富植酸钝化液中不含铬,废液中不会产生铬污染。     

In Situ Laser Coating of Calcium Phosphate on TC4 Surface for Enhancing Bioactivity

 Titanium alloy has been a successful implant material owing to its excellent ratio of strength to weight, toughness, and bio inert oxide surface. Significant progress has been made in improving the bioactivity of titanium alloy by coating its oxide surface with calcium phosphates. In the present study, in situ coating was reported on Ti6Al4V(TC4) surface with calcium phosphate (Ca P) bioceramics synthesized and synchronously cladded by laser beam. This coating was grown by first preplacing directly the raw powders, which contain 80% of CaHPO4·2H2O, 20% of CaCO3, and dram of rare earth (RE), on the TC4 surfaces, and then exposing the surfaces to the laser beam with a power density of 1273-1527 MW·m-2 and a scanning velocity of 105 m/s. The resultant coating was characterized using scanning electron microscopy (SEM), X ray diffraction (XRD), thermogravimetric analysis and Different thermal Scanning (TG DSC), and Energy Dispersive X ray Detection (EDX). The results show that these laser ceramics include hydroxyapatite (HA), tricalcium phosphate (TCP), Ca2P2O7, and other Ca P phases, and the interface between the coating and the TC4 substrate has tighter fixation, in which the chemical bonding is approved. These laser hybrid coatings are useful in enhancing the bioactivity of titanium alloy surfaces.     

固相反应条件对磷酸铁锂电化学性能的影响

以碳酸锂(Li₂CO₃)为锂源, 磷酸二氢铵(NH₄H₂PO₄)为磷源, 草酸亚铁(FeC₂O₄·2H₂O)为铁源, 柠檬酸(C₆H₈O₇·H₂O)为碳源, 采用固相反应法制备橄榄石晶型磷酸铁锂。利用X射线衍射仪, 扫描电子显微镜, 能谱仪, 比表面积分析仪和电化学测试等设备和方法对磷酸铁锂材料的物相组成、结构、形貌和电化学性能进行表征, 研究煅烧温度和保温时间对磷酸铁锂电化学性能的影响, 并通过添加碳对试样进行包覆改性。结果表明, 在煅烧温度为700℃, 保温时间为12 h条件下制备的磷酸铁锂正极材料的电化学性能良好, 碳包覆能有效改善电极材料的性能。包覆碳后的磷酸铁锂电极材料在0.2C充电电流密度下首次放电比容量可达319.2 mAh·g-1; 在1C充电电流密度下循环100次后, 放电比容量保持在168.1 mAh·g-1。     

类松果状NiMoO4/MnO2复合材料的合成及超级电容性能

以Na₂MoO₄·2H₂O、NiSO₄·6H₂O和MnO₂为原料, 采用水热法成功制备了类松果状NiMoO₄/MnO₂复合材料.通过X射线衍射、扫描电子显微镜、恒电流充放电、循环伏安和交流阻抗对材料进行表征.结果表明, MnO₂的最佳质量分数为10%, 所得NiMoO₄/MnO₂复合材料具有类松果状形貌, 其颗粒直径为200~600 nm, 且表面粗糙、多孔; 在1 A·g-1的电流密度下, MnO₂质量分数为0、5%、10%、15%、20%时, 所得复合材料NM0、NM5、NM10、NM15和NM20的放电比电容分别为260、248、650、420和305 F·g-1.在电流密度为10 A·g-1下, 最佳样品NM10复合材料的首次放电比容量为102 F·g-1, 经过100次循环后, 其放电比电容稳定在147 F·g-1.该性能的提高, 主要是由于MnO₂的引入弥补了NiMoO₄单一材料存在的不足, 从而达到协同增效的作用.      

CaO基含V2O5及TiO2脱磷终渣磷酸盐赋存形式

以Ca O基含V₂O₅、Ti O₂脱磷终渣为研究对象, 采用共存理论建立磷富集程度R_ci-cj模型, 并与实际渣系的磷酸盐赋存形式进行对比研究.结果表明:随着碱度的增加, 3CaO·P₂O₅的质量作用浓度逐渐降低, 4CaO·P₂O₅的质量作用浓度逐渐增加, 而2CaO·Si O₂的质量作用浓度呈现出先增加后降低的趋势;C₃P+C₄P的富集可能性范围87%⁹4%, C₂S既是主要的硅酸钙化合物也是形成富磷产物必不可少的物质, 磷酸盐富集相中主要以C₂S-C₃P和C₂S-C₄P的形式存在于炉渣中, 结合扫描电镜 (SEM) 结果、X射线衍射 (XRD) 分析与假设, 计算可得深灰色富磷区域内的含P₂O₅固溶体为2CaO·Si O₂-3CaO·P₂O₅和2CaO·Si O₂-4CaO·P₂O₅, 此结果与理论计算相吻合.